US20220144977A1 - Production method for modified vinyl alcohol-based polymer particles and particles obtained using same - Google Patents
Production method for modified vinyl alcohol-based polymer particles and particles obtained using same Download PDFInfo
- Publication number
- US20220144977A1 US20220144977A1 US17/438,697 US202017438697A US2022144977A1 US 20220144977 A1 US20220144977 A1 US 20220144977A1 US 202017438697 A US202017438697 A US 202017438697A US 2022144977 A1 US2022144977 A1 US 2022144977A1
- Authority
- US
- United States
- Prior art keywords
- vinyl alcohol
- based polymer
- polymer particles
- mass
- modified vinyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000002245 particle Substances 0.000 title claims abstract description 244
- 229920000642 polymer Polymers 0.000 title claims abstract description 227
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical class OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 title claims abstract description 222
- 238000004519 manufacturing process Methods 0.000 title abstract description 15
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 46
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 29
- 239000011593 sulfur Substances 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000003377 acid catalyst Substances 0.000 claims abstract description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 48
- 150000002148 esters Chemical group 0.000 claims description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 18
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- 150000001735 carboxylic acids Chemical class 0.000 claims 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 36
- 239000007788 liquid Substances 0.000 abstract description 23
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 125000004185 ester group Chemical group 0.000 abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 26
- 150000002430 hydrocarbons Chemical group 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 23
- -1 contact lenses Substances 0.000 description 23
- 239000002904 solvent Substances 0.000 description 21
- 238000006116 polymerization reaction Methods 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- 238000011156 evaluation Methods 0.000 description 18
- 239000000945 filler Substances 0.000 description 17
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 238000007127 saponification reaction Methods 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 238000012916 structural analysis Methods 0.000 description 11
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 238000005342 ion exchange Methods 0.000 description 9
- 239000000178 monomer Chemical group 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 8
- 230000009257 reactivity Effects 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 0 *CC(*)OC(=O)C/C(C)=C/[Y] Chemical compound *CC(*)OC(=O)C/C(C)=C/[Y] 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 238000010828 elution Methods 0.000 description 6
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 206010034972 Photosensitivity reaction Diseases 0.000 description 5
- 150000001336 alkenes Chemical group 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 230000036211 photosensitivity Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000005809 transesterification reaction Methods 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 4
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- 239000012456 homogeneous solution Substances 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 4
- FBJHFBMPCFWYBM-UHFFFAOYSA-N C/C(=C\[Y])CC(=O)O Chemical compound C/C(=C\[Y])CC(=O)O FBJHFBMPCFWYBM-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 125000002993 cycloalkylene group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
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- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 229960002703 undecylenic acid Drugs 0.000 description 2
- OYTMDOROMQJKMQ-UHFFFAOYSA-N (2-acetyloxy-3-ethenoxypropyl) acetate Chemical compound CC(=O)OCC(OC(C)=O)COC=C OYTMDOROMQJKMQ-UHFFFAOYSA-N 0.000 description 1
- XKZKQTCECFWKBN-VOTSOKGWSA-N (e)-dec-4-enoic acid Chemical compound CCCCC\C=C\CCC(O)=O XKZKQTCECFWKBN-VOTSOKGWSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- ICCVOKMKWYGITK-UHFFFAOYSA-N 1-(2-methylprop-2-enoylamino)propane-1-sulfonic acid Chemical compound CCC(S(O)(=O)=O)NC(=O)C(C)=C ICCVOKMKWYGITK-UHFFFAOYSA-N 0.000 description 1
- IAUGBVWVWDTCJV-UHFFFAOYSA-N 1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CCC(S(O)(=O)=O)NC(=O)C=C IAUGBVWVWDTCJV-UHFFFAOYSA-N 0.000 description 1
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 description 1
- QJJDJWUCRAPCOL-UHFFFAOYSA-N 1-ethenoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOC=C QJJDJWUCRAPCOL-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- HVRZYSHVZOELOH-UHFFFAOYSA-N 2-Methyl-4-pentenoic acid Chemical compound OC(=O)C(C)CC=C HVRZYSHVZOELOH-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- PGYJSURPYAAOMM-UHFFFAOYSA-N 2-ethenoxy-2-methylpropane Chemical compound CC(C)(C)OC=C PGYJSURPYAAOMM-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- FYYOTZLMLLTWAP-UHFFFAOYSA-N 3,3-dimethylpent-4-enoic acid Chemical compound C=CC(C)(C)CC(O)=O FYYOTZLMLLTWAP-UHFFFAOYSA-N 0.000 description 1
- OZYYQTRHHXLTKX-UHFFFAOYSA-N 7-octenoic acid Chemical compound OC(=O)CCCCCC=C OZYYQTRHHXLTKX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 1
- IGRURXZWJCSNKU-UHFFFAOYSA-N Isopropenylacetic acid Chemical compound CC(=C)CC(O)=O IGRURXZWJCSNKU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004976 cyclobutylene group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004979 cyclopentylene group Chemical group 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004980 cyclopropylene group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- XUDOZULIAWNMIU-UHFFFAOYSA-N delta-hexenoic acid Chemical compound OC(=O)CCCC=C XUDOZULIAWNMIU-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- LPUZTLKYAOOFDX-QXMHVHEDSA-N ethenyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC=C LPUZTLKYAOOFDX-QXMHVHEDSA-N 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- WNMORWGTPVWAIB-UHFFFAOYSA-N ethenyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC=C WNMORWGTPVWAIB-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- UJRIYYLGNDXVTA-UHFFFAOYSA-N ethenyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OC=C UJRIYYLGNDXVTA-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- QBDADGJLZNIRFQ-UHFFFAOYSA-N ethenyl octanoate Chemical compound CCCCCCCC(=O)OC=C QBDADGJLZNIRFQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- YKLKUNBKAPXTEZ-UHFFFAOYSA-M methyl carbonate;tetramethylazanium Chemical compound COC([O-])=O.C[N+](C)(C)C YKLKUNBKAPXTEZ-UHFFFAOYSA-M 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- YMDZGJOTVBKZQK-UHFFFAOYSA-N n,n-dimethylpropan-1-amine;2-methylprop-2-enamide Chemical compound CCCN(C)C.CC(=C)C(N)=O YMDZGJOTVBKZQK-UHFFFAOYSA-N 0.000 description 1
- QQGJWWNPACORPU-UHFFFAOYSA-N n,n-dimethylpropan-1-amine;prop-2-enamide Chemical compound NC(=O)C=C.CCCN(C)C QQGJWWNPACORPU-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- ZIWDVJPPVMGJGR-UHFFFAOYSA-N n-ethyl-2-methylprop-2-enamide Chemical compound CCNC(=O)C(C)=C ZIWDVJPPVMGJGR-UHFFFAOYSA-N 0.000 description 1
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920000247 superabsorbent polymer Polymers 0.000 description 1
- 239000004583 superabsorbent polymers (SAPs) Substances 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- XKZKQTCECFWKBN-UHFFFAOYSA-N trans-4-decenoic acid Natural products CCCCCC=CCCC(O)=O XKZKQTCECFWKBN-UHFFFAOYSA-N 0.000 description 1
- UIUWNILCHFBLEQ-NSCUHMNNSA-N trans-pent-3-enoic acid Chemical compound C\C=C\CC(O)=O UIUWNILCHFBLEQ-NSCUHMNNSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F16/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
- C08F16/04—Acyclic compounds
- C08F16/06—Polyvinyl alcohol ; Vinyl alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
- C08F216/04—Acyclic compounds
- C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2029/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof as moulding material
- B29K2029/04—PVOH, i.e. polyvinyl alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2810/00—Chemical modification of a polymer
- C08F2810/30—Chemical modification of a polymer leading to the formation or introduction of aliphatic or alicyclic unsaturated groups
Definitions
- the present invention relates to a method of producing modified vinyl alcohol-based polymer particles having an unsaturated hydrocarbon group in a side chain and to particles obtained by the same.
- Vinyl alcohol-based polymers represented by polyvinyl alcohol have excellent interfacial properties and strength properties as those of a limited number of crystalline water-soluble polymers, and thus are used for paper processing, fiber processing, emulsion stabilizers, and the like.
- Vinyl alcohol-based polymer gels obtained by crosslinking such a vinyl alcohol-based polymer by various methods are used for, due to their hydrophilicity and safety, super absorbent polymers, contact lenses, aqueous/organic solvent-based SEC column fillers, and the like.
- vinyl alcohol-based polymers having a vinyl alcohol unit content of 95 mol % or more exhibit high hydrophilicity as column fillers, and films and fiber obtained using an aqueous solution of such a vinyl alcohol-based polymer have excellent strength.
- attempts are made to introduce a functional group and the like into the vinyl alcohol-based polymer and various modified vinyl alcohol-based copolymers are developed.
- modified vinyl alcohol-based polymers having an unsaturated hydrocarbon group introduced into a side chain may be subjected to impartation of water resistance by crosslinking by high-energy beam radiation, modification by graft polymerization, and the like.
- a method of introducing an unsaturated hydrocarbon group into a side chain a generally used method causes the hydroxyl group in the vinyl alcohol-based polymer to be reacted with various compounds.
- Patent Document 1 discloses a method of synthesizing a vinyl alcohol-based polymer containing an unsaturated hydrocarbon group by acetalization using aldehyde having an unsaturated hydrocarbon group.
- Patent Document 2 discloses a method of synthesizing a vinyl alcohol-based polymer containing an unsaturated hydrocarbon group by etherification using an epoxy compound having an unsaturated hydrocarbon group.
- some among compounds such as aldehyde and epoxy are considered to have mutagenicity and there is a demand for a method not using these compounds.
- Patent Documents 3 and 4 disclose methods of obtaining a modified vinyl alcohol-based polymer comprising: dissolving a vinyl alcohol-based polymer in dimethyl sulfoxide (DMSO), followed by transesterification with unsaturated carboxylic ester; and then precipitation in a poor solvent.
- Patent Document 5 describes a method comprising: dissolving a vinyl alcohol-based polymer in water; and then esterifying with unsaturated carboxylic acid and an acid catalyst to produce a solution containing a modified vinyl alcohol-based polymer.
- Non-Patent Document 1 discloses a method of obtaining a modified vinyl alcohol-based polymer comprising: dissolving a vinyl alcohol-based polymer in water; followed by esterification with unsaturated carboxylic acid, acetic acid, and an acid catalyst; and then precipitation in a poor solvent.
- the present inventors also find a problem that, having extremely high affinity for vinyl alcohol-based polymers, DMSO is likely to remain in the resin even when precipitated in a poor solvent.
- DMSO is likely to remain in the resin even when precipitated in a poor solvent.
- use of the vinyl alcohol-based polymer thus obtained as a column filler has a problem that the sulfur content is eluted over time to cause contamination.
- Patent Document 5 Use water, not DMSO as the solvent for esterification, the methods of producing a modified vinyl alcohol-based polymer described in Patent Document 5 and Non-Patent Document 1 can solve the problem of the residual sulfur content while, to isolate the modified vinyl alcohol-based polymer, the polymer has to be precipitated in a large amount of poor solvent after esterification, causing extreme complication and economic disadvantages.
- precipitating a polymer by such a method it is difficult to control the shape of particles and it is also found that use of the polymer thus obtained as a column filler causes problems of poor liquid flow and the like.
- Patent Document 5 only discloses the solution containing a modified vinyl alcohol-based polymer and does not disclose the particle shape at all.
- the present invention has been made to solve the above problems, and it is an object thereof to provide a method of producing modified vinyl alcohol-based polymer particles having an unsaturated hydrocarbon group that is capable of controlling the particle shape and has excellent cost efficiency. It is also an object thereof to provide modified vinyl alcohol-based polymer particles having an unsaturated hydrocarbon group that have a low sulfur content, and have an average particle diameter in a predetermined range.
- the present inventors have been studied intensively to solve the above problems, and as a result, they have found the following. That is, that reaction of unsaturated carboxylic acid with vinyl alcohol-based polymer particles by mixing vinyl alcohol-based polymer particles with a mixed medium containing unsaturated carboxylic acid, an acid catalyst, and water allows not only omitting precipitation in a large amount of poor solvent for isolation of the reaction product but also controlling the particle shape of the modified vinyl alcohol-based polymer to be obtained. They have also found that reduction in the sulfur content reduces the odor while the modified vinyl alcohol-based polymer particles are used in the form of an aqueous solution.
- modified vinyl alcohol-based polymer particles having an average particle diameter in a specific range and also having a reduced sulfur content allow the problems of liquid flowability and contamination to be solved when the modified vinyl alcohol-based polymer particles are used as a column filler, and thus have come to complete the present invention.
- the unsaturated carboxylic acid is represented by a formula (1) below, and,
- modified vinyl alcohol-based polymer particles containing a vinyl ester unit represented by a formula (2) below, having a vinyl alcohol unit content based on the total constitutional units from 95 to 99.99 mol %, and having an average particle diameter from 50 to 2000 ⁇ m,
- X denotes a carbon-carbon bond or a divalent saturated hydrocarbon group having a carbon number from 1 to 10 optionally having a branched structure
- Y denotes a hydrogen atom or a saturated hydrocarbon group having a carbon number from 1 to 6 optionally having a branched structure
- Z denotes a hydrogen atom or a methyl group
- the modified vinyl alcohol-based polymer particles have a specific surface area from 0.01 to 1.0 m 2 /g. It is also preferred that the mixed medium has a water content from 1 to 30 mass %. It is also preferred that the mixed medium further contains acetic acid. It is also preferred that Y denotes a hydrogen atom. It is also preferred that X denotes a carbon-carbon bond.
- the production method preferably further comprises washing the modified vinyl alcohol-based polymer particles.
- modified vinyl alcohol-based polymer particles comprising a vinyl ester unit represented by a formula (2) below, wherein a vinyl alcohol unit content is from 95 to 99.99 mol % and a sulfur content is from 0.01 to 20000 ppm based on the total constitutional units, and an average particle diameter is from 50 to 2000 ⁇ m:
- X denotes a carbon-carbon bond or a divalent saturated hydrocarbon group having a carbon number from 1 to 10 optionally having a branched structure
- Y denotes a hydrogen atom or a saturated hydrocarbon group having a carbon number from 1 to 6 optionally having a branched structure
- Z denotes a hydrogen atom or a methyl group.
- a ratio of three or more consecutive vinyl ester units to the total vinyl ester units is 10 mol % or less in the modified vinyl alcohol-based polymer. It is also preferred that a yellow index (YI) of the modified vinyl alcohol-based polymer particles measured in accordance with ASTM D1925 is 50 or less. It is also preferred that a content of the vinyl ester unit represented by the formula (2) based on the total constitutional units in the modified vinyl alcohol-based polymer particles is from 0.01 to 5 mol %. It is also preferred that Y denotes a hydrogen atom. It is also preferred that X denotes a carbon-carbon bond.
- the method of producing modified vinyl alcohol-based polymer particles of the present invention does not cause the problem of the residual sulfur content derived from a liquid medium used for reaction and the like and is also capable of modifying the vinyl alcohol-based polymer particles while maintaining the particle shape, and thus the method needs no process for precipitating the polymer in a large amount of poor solvent, thereby being convenient and economically excellent.
- the modified vinyl alcohol-based polymer particles of the present invention have a low sulfur content, have excellent high-energy beam reactivity, and have an average particle diameter in a predetermined range, and thus are preferably used for a column filler and the like.
- the modified vinyl alcohol-based polymer particles cause less odor for production of films and fiber while the particles are used in the form of an aqueous solution.
- the present invention is a method of producing modified vinyl alcohol-based polymer particles, comprising mixing vinyl alcohol-based polymer particles with a mixed medium containing unsaturated carboxylic acid, an acid catalyst, and water, wherein
- the unsaturated carboxylic acid is represented by a formula (1) below, and,
- modified vinyl alcohol-based polymer particles containing a vinyl ester unit represented by a formula (2) below, having a vinyl alcohol unit content based on the total constitutional units from 95 to 99.99 mol %, and having an average particle diameter from 50 to 2000 ⁇ m,
- X denotes a carbon-carbon bond or a divalent saturated hydrocarbon group having a carbon number from 1 to 10 optionally having a branched structure
- Y denotes a hydrogen atom or a saturated hydrocarbon group having a carbon number from 1 to 6 optionally having a branched structure
- Z denotes a hydrogen atom or a methyl group
- X in the formula (1) denotes a carbon-carbon bond or a divalent saturated hydrocarbon group having a carbon number from 1 to 10 optionally having a branched structure. From the perspective of high-energy beam reactivity, it is preferred that X denotes a carbon-carbon bond.
- Specific examples of the unsaturated carboxylic acid when X denotes a carbon-carbon bond include methacrylic acid, acrylic acid, crotonic acid, and the like.
- the saturated hydrocarbon group used as X has a carbon number from 1 to 10.
- the carbon number of more than 10 causes worsening of water solubility.
- the carbon number is preferably 5 or less, more preferably 3 or less, and even more preferably 2 or less.
- Examples of the divalent saturated hydrocarbon group used as X include alkylene groups, cycloalkylene groups, and the like.
- Examples of the alkylene groups include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, and the like.
- Examples of the cycloalkylene groups include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and the like.
- the alkylene groups and the cycloalkylene groups used as X optionally have an alkyl group, such as a methyl group and an ethyl group, as the branched structure.
- Y in the formula (1) denotes a hydrogen atom or a saturated hydrocarbon group having a carbon number from 1 to 6 optionally having a branched structure. It is preferred that Y denotes a hydrogen atom.
- the saturated hydrocarbon group used as Y has a carbon number from 1 to 6.
- the carbon number of more than 6 has a risk of causing worsening of water solubility.
- the carbon number is preferably 5 or less, more preferably 3 or less, and even more preferably 2 or less.
- Examples of the saturated hydrocarbon group used as Y include alkyl groups, cycloalkyl groups, and the like.
- alkyl groups include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, and the like.
- cycloalkyl groups examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like.
- the alkyl groups and the cycloalkyl groups used as Y optionally have an alkyl group, such as a methyl group and an ethyl group, as the branched structure.
- the unsaturated carboxylic acid represented by the formula (1) include methacrylic acid, acrylic acid, crotonic acid, 3-methyl-3-butenoic acid, 4-pentenoic acid, 2-methyl-4-pentenoic acid, 5-hexenoic acid, 3,3-dimethyl-4-pentenoic acid, 7-octenoic acid, trans-3-pentenoic acid, trans-4-decenoic acid, 10-undecenoic acid, and the like.
- methacrylic acid, acrylic acid, 4-pentenoic acid, and 10-undecenoic acid are preferred.
- an acid catalyst is used as the catalyst for reaction of vinyl alcohol-based polymer particles with the unsaturated carboxylic acid. This accelerates the reaction of the vinyl alcohol-based polymer particles with the unsaturated carboxylic acid.
- the acid catalyst may catalyze dehydration esterification of the unsaturated carboxylic acid represented by the formula (1) and the hydroxyl groups in the vinyl alcohol-based polymer particles, and either of organic acid and inorganic acid may be used.
- the organic acid include methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and paratoluenesulfonic acid.
- Examples of the inorganic acid include sulfuric acid, hydrochloric acid, and nitric acid. Among all, methanesulfonic acid, paratoluenesulfonic acid, and sulfuric acid are preferred, and paratoluenesulfonic acid is particularly preferred.
- the vinyl alcohol-based polymer constituting the vinyl alcohol-based polymer particles used in the present invention preferably has a degree of saponification from 95 to 99.99 mol %.
- the vinyl alcohol-based polymer preferably has a viscosity-average degree of polymerization from 100 to 5000 and more preferably from 200 to 4000.
- a viscosity-average degree of polymerization of less than 100 has a risk of reducing the mechanical strength of a modified vinyl alcohol-based polymer to be obtained.
- a viscosity-average degree of polymerization of more than 5000 has a risk of causing difficulty in industrial production of the vinyl alcohol-based polymer particles.
- the degree of saponification and the viscosity-average degree of polymerization of the vinyl alcohol-based polymer are measured in accordance with JIS K6726.
- the vinyl alcohol units in the vinyl alcohol-based polymer may be derived from vinyl ester units by hydrolysis, alcoholysis, and the like. Accordingly, depending on the conditions for conversion from vinyl ester units to vinyl alcohol units and the like, vinyl ester units sometimes remain in the vinyl alcohol-based polymer.
- vinyl ester of the vinyl ester units examples include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate, vinyl benzoate, and the like.
- vinyl acetate is preferred from an industrial perspective.
- the vinyl alcohol-based polymer may contain vinyl alcohol units and monomer units other than the vinyl ester units.
- examples of such another monomer unit include those derived from ethylenic unsaturated monomers copolymerizable with vinyl ester.
- Examples of such an ethylenic unsaturated monomer include: ⁇ -olefins, such as ethylene, propylene, n-butene, isobutylene, and 1-hexene, acrylic acid and salts thereof; acrylic esters, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, and octadecyl acrylate; methacrylic acid and salts thereof; methacrylic esters, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-buty
- the contents of the vinyl alcohol units and the monomer units other than the vinyl ester units in the vinyl alcohol-based polymer is usually 10 mol % or less, preferably 5 mol % or less, and more preferably 1 mol % or less.
- the vinyl alcohol-based polymer particles used in the present invention preferably has an average particle diameter from 50 to 2000 ⁇ m.
- An average particle diameter of less than 50 ⁇ m has a risk of causing insufficient liquid flow when modified vinyl alcohol-based polymer particles thus obtained are used as a column filler.
- the average particle diameter is more preferably 100 ⁇ m or more, even more preferably 200 ⁇ m or more, particularly preferably 300 ⁇ m or more, and most preferably 500 ⁇ m or more. Meanwhile, an average particle diameter of more than 2000 ⁇ m, there is a risk that reaction does not uniformly proceed inside and outside the particles.
- the average particle diameter is more preferably 900 ⁇ m or less and even more preferably 800 ⁇ m or less.
- the vinyl alcohol-based polymer particles By mixing the vinyl alcohol-based polymer particles with a mixed medium containing the unsaturated carboxylic acid represented by the formula (1), the acid catalyst, and water, the vinyl alcohol-based polymer particles are reacted with the unsaturated carboxylic acid to obtain modified vinyl alcohol-based polymer particles.
- the vinyl alcohol-based polymer particles are thus reacted with the unsaturated carboxylic acid, that is, reaction is carried out while maintaining the particle shape of the vinyl alcohol-based polymer particles as a raw material, thereby allowing not only omitting precipitation in a large amount of poor solvent for isolation of the reaction product but also controlling the particle shape of the modified vinyl alcohol-based polymer particles.
- a sulfur content derived from a liquid medium used for reaction and the like remains in the modified vinyl alcohol-based polymer particles.
- a ratio of three or more consecutive vinyl ester units is reduced and thus viscosity stability used in the form of an aqueous solution is improved.
- a preferred method comprises: mixing the vinyl alcohol-based polymer particles with the mixed medium; thereby dispersing the vinyl alcohol-based polymer particles in the mixed medium to react the vinyl alcohol-based polymer particles with the unsaturated carboxylic acid.
- a specific example includes a method comprising: mixing the vinyl alcohol-based polymer particles with the mixed medium to form a slurry or a dispersion; thereby reacting the vinyl alcohol-based polymer particles with the unsaturated carboxylic acid.
- Other examples include a method comprising: uniformly blending the vinyl alcohol-based polymer particles with the mixed medium; thereby reacting the vinyl alcohol-based polymer particles with the unsaturated carboxylic acid, and the like.
- a method of mixing the vinyl alcohol-based polymer particles with the mixed medium is not particularly limited as long as it is capable of uniformly mixing both. Specific examples include (1) a method comprising: preparing the mixed medium; and then mixing the vinyl alcohol-based polymer particles with the mixed medium, (2) a method comprising: mixing the vinyl alcohol-based polymer with some components of the mixed medium; and then mixing a mixture thus obtained with the rest of the components of the mixed medium, (3) a method comprising: simultaneously mixing each component of the mixed medium with the vinyl alcohol-based polymer particles, and the like, and among all, (1) is preferred.
- a mass ratio [polymer particles/mixed medium] of the vinyl alcohol-based polymer particles to the mixed medium for mixing the vinyl alcohol-based polymer particles with the mixed medium is preferably from 3/97 to 90/10.
- a mass ratio [polymer particles/mixed medium] of less than 3/97 has a risk of severely reducing the reactivity.
- the mass ratio [polymer particles/mixed medium] is more preferably 10/90 or more.
- a mass ratio [polymer particles/mixed medium] of more than 90/10 has a risk of not allowing uniform mixing of the vinyl alcohol-based polymer particles with the mixed medium and a risk of severely reducing the reactivity.
- the mass ratio [polymer particles/mixed medium] is more preferably 80/20 or less and even more preferably 50/50 or less.
- a water content in the mixed medium is preferably from 1 to 30 mass %.
- a water content of less than 1 mass % has a risk that the modified vinyl alcohol-based polymer particles to be obtained is likely to be colored.
- the water content is more preferably 3 mass % or more, even more preferably 5 mass % or more, and particularly preferably 8 mass % or more.
- a water content of more than 30 mass % has a risk of dissolving the vinyl alcohol-based polymer during reaction, causing difficulty in modification of the vinyl alcohol-based polymer particles while maintaining the particle shape.
- the water content is more preferably 20 mass % or less and even more preferably 18 mass % or less.
- an amount of the acid catalyst to be added is preferably from 0.0001 to 0.1 mol per mol of hydroxyl group in the vinyl alcohol-based polymer.
- the amount to be added is more preferably 0.0005 mol or more. Meanwhile, the amount to be added is more preferably 0.08 mol or less.
- a content of the unsaturated carboxylic acid in the mixed medium is preferably from 5 to 2000 parts by mass based on 100 parts by mass of the vinyl alcohol-based polymer particles.
- An amount of the unsaturated carboxylic acid to be added of less than 5 parts by mass has a risk of reducing the reactivity.
- the content of the unsaturated carboxylic acid is more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, and particularly preferably 30 parts by mass or more. Meanwhile, a content of the unsaturated carboxylic acid of more than 2000 parts by mass has a risk of increasing unreacted unsaturated carboxylic acid and increasing the costs.
- the content of the unsaturated carboxylic acid is more preferably 1500 parts by mass or less, even more preferably 1000 parts by mass or less, and particularly preferably 700 parts by mass or less.
- the mixed medium preferably further contains acetic acid.
- a content of the acetic acid in the mixed medium is preferably from 1 to 1000 parts by mass based on 100 parts by mass of water in the mixed medium.
- the content of the acetic acid is more preferably 5 parts by mass or more and even more preferably 10 parts by mass or more.
- the content of the acetic acid is more preferably 800 parts by mass or less and even more preferably 600 parts by mass or less.
- the mixed medium may contain additives other than the unsaturated carboxylic acid represented by the formula (1), the acid catalyst, water, and acetic acid.
- an additive include surfactants and organic solvents.
- the surfactant include: nonionic surfactants, such as polyoxyethylene-alkyl ether type, polyoxyethylene-alkyl phenol type, polyoxyethylene-polyhydric alcohol ester type, esters of polyhydric alcohol and fatty acid, and oxyethylene-oxypropylene block polymers; anionic surfactants, such as higher alcohol sulfate, alkali salt of higher fatty acid, polyoxyethylene alkylphenol ether sulfate, alkylbenzene sulfonate, naphthalene sulfonate formalin condensate, alkyl diphenyl ether sulfonate, dialkyl sulfosuccinate, and higher alcohol phosphate salt; and reactive surfactants.
- organic solvent examples include: alcohols, such as methanol, ethanol, propanol, and butanol; aliphatic or alicyclic hydrocarbons, such as n-hexane, n-pentane, and cyclohexane; aromatic hydrocarbons, such as benzene and toluene; nitriles, such as acetonitrile and benzonitrile; ethers, such as diethyl ether, diphenyl ether, anisole, 1,2-dimethoxyethane, and 1,4-dioxane; ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone, and methyl isobutyl ketone; esters, such as methyl acetate, ethyl acetate, and ethyl propionate; and the like.
- alcohols such as methanol, ethanol, propanol, and butanol
- Examples of such another additive also include ultraviolet absorbers, light stabilizers, antioxidants, plasticizers, and defoamers.
- the content of these other additives in the mixed medium is preferably 50 mass % or less and more preferably 35 mass % or less.
- the mixed medium preferably does not contain a liquid medium containing sulfur.
- a temperature for reacting the vinyl alcohol-based polymer particles with the unsaturated carboxylic acid is preferably from 10° C. to 120° C.
- the temperature is more preferably 30° C. or more and even more preferably 50° C. or more. Meanwhile, the temperature is more preferably 100° C. or less and even more preferably 90° C. or less.
- Reaction time for reacting the vinyl alcohol-based polymer particles with the unsaturated carboxylic acid is usually from 0.5 to 72 hours.
- the specific washing method include a method comprising washing the particles with a solvent.
- Specific examples include a method comprising: immersing the particles in a solvent; and then draining, a method comprising circulating a solvent in a washing column while contacting the particles with the solvent for washing, a method comprising flowing the particles while spraying a washing solvent, and the like.
- Examples of the solvent to be used include: alcohols, such as methanol, ethanol, propanol, and butanol; aliphatic and alicyclic hydrocarbons, such as n-hexane, n-pentane, and cyclohexane; aromatic hydrocarbons, such as benzene and toluene; nitriles, such as acetonitrile and benzonitrile; ethers, such as diethyl ether, diphenyl ether, anisole, 1,2-dimethoxyethane, and 1,4-dioxane; ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone, and methyl isobutyl ketone; esters, such as methyl acetate, ethyl acetate, and ethyl propionate; and the like.
- alcohols such as methanol, ethanol, propanol, and butano
- alcohols, ethers, ketones, and esters are more preferred, methanol, ethanol, propanol, diethyl ether, 1,2-dimethoxyethane, acetone, methyl ethyl ketone, methyl acetate, and ethyl acetate are even more preferred, and methanol, propanol, acetone, methyl ethyl ketone, methyl acetate, and ethyl acetate are particularly preferred.
- One type of these organic solvents may be used singly or two or more types of them may be used together.
- the drying temperature is from 20° C. to 150° C. and the drying time is from 1 to 72 hours.
- the modified vinyl alcohol-based polymer particles may be dried under atmospheric pressures or under reduced pressures.
- the modified vinyl alcohol-based polymer particles thus obtained have to have an average particle diameter from 50 to 2000 ⁇ m.
- the modified vinyl alcohol-based polymer particles having such an average particle diameter are excellent in liquid flowability and the like when used as a column filler.
- the production method of the present invention facilitates controlling the particle shape of the modified vinyl alcohol-based polymer and thus allows convenient production of the modified vinyl alcohol-based polymer particles having such an average particle diameter.
- An average particle diameter of less than 50 ⁇ m causes insufficient liquid flow when the modified vinyl alcohol-based polymer particles thus obtained are used as a column filler.
- the average particle diameter is preferably 100 ⁇ m or more, more preferably 200 ⁇ m or more, even more preferably 300 ⁇ m or more, and particularly preferably 500 ⁇ m or more.
- an average particle diameter of more than 2000 ⁇ m causes reaction not to uniformly proceed inside and outside the particles during production of the modified vinyl alcohol-based polymer particles.
- the average particle diameter is preferably 900 ⁇ m or less and more preferably 800
- the modified vinyl alcohol-based polymer particles obtained have a specific surface area from 0.01 to 1.0 m 2 /g.
- a specific surface area of less than 0.01 m 2 /g has a risk of worsening separation performance when used as a column filler.
- the specific surface area is more preferably 0.1 m 2 /g or more.
- a specific surface area of more than 1.0 m 2 /g has a risk of causing consolidation of the particles and poor filtration when used as a column filler.
- the modified vinyl alcohol-based polymer particles thus obtained preferably has a ratio of three or more consecutive vinyl ester units to the total vinyl ester units of 10 mol % or less.
- the ratio is more preferably 9 mol % or less, even more preferably 8 mol % or less, and particularly preferably 7 mol % or less.
- the ratio of three or more consecutive vinyl ester units is usually 0.1 mol % or more. It is possible to obtain the ratio of three or more consecutive vinyl ester units by a method using 1 H-NMR measurement described later in Examples.
- the modified vinyl alcohol-based polymer thus obtained has to have a vinyl alcohol unit content based on the total constitutional units from 95 to 99.99 mol %.
- a vinyl alcohol unit content of less than 95 mol % has a risk of severely reducing the crystallinity of the modified vinyl alcohol-based polymer and reducing the mechanical strength.
- the vinyl alcohol unit content is more preferably 95.5 mol % or more.
- a vinyl alcohol unit content of more than 99.99 mol % has a risk of causing difficulty in industrial production of the modified vinyl alcohol-based polymer.
- the vinyl alcohol unit content is preferably 99.9 mol % or less.
- the modified vinyl alcohol-based polymer particles thus obtained preferably has a content of a vinyl ester unit represented by the formula (2) from 0.01 to 5 mol % based on the total constitutional units.
- a content of the vinyl ester units of less than 0.01 mol % has a risk that crosslinking reaction does not sufficiently proceed during crosslinking reaction of the modified vinyl alcohol-based polymer particles.
- the content of the vinyl ester units is more preferably 0.05 mol % or more, even more preferably 0.3 mol % or more, and particularly preferably 0.5 mol % or more.
- a content of the vinyl ester units of more than 5 mol % has a risk of causing worsening of water solubility of the modified vinyl alcohol-based polymer particles. It is possible to obtain the content of the vinyl ester unit represented by the formula (2) by a method using 1 H-NMR measurement described later in Examples.
- the modified vinyl alcohol-based polymer particles thus obtained may contain vinyl alcohol units and monomer units other than the vinyl ester units.
- Examples of such another monomer unit include those described above as the monomer units other than vinyl alcohol units and vinyl ester units contained in the vinyl alcohol-based polymer particles used for production of the modified vinyl alcohol-based polymer particles.
- the content of the monomer units other than the vinyl alcohol units and the vinyl ester units in the modified vinyl alcohol-based polymer particles is usually 10 mol % or less, preferably 5 mol % or less, and more preferably 1 mol % or less.
- the modified vinyl alcohol-based polymer particles thus obtained preferably has a viscosity-average degree of polymerization from 100 to 5000 and more preferably from 200 to 4000.
- a viscosity-average degree of polymerization of less than 100 has a risk of reducing the mechanical strength of the modified vinyl alcohol-based polymer particles thus obtained.
- a viscosity-average degree of polymerization of more than 5000 has a risk of causing difficulty in industrial production of the vinyl alcohol-based polymer particles.
- the viscosity-average degree of polymerization of the modified vinyl alcohol-based polymer particles is measured in accordance with JIS K6726.
- the sulfur content in the modified vinyl alcohol-based polymer particles thus obtained is preferably from 0.01 to 20000 ppm.
- the modified vinyl alcohol-based polymer particles having such a low sulfur content is less likely to cause a problem of contamination due to elution of the sulfur content when used as a column filler.
- the modified vinyl alcohol-based polymer particles also cause less odor when used in the form of an aqueous solution.
- the sulfur content is more preferably 10000 ppm or less, even more preferably 5000 ppm or less, and particularly preferably 3000 ppm or less. Meanwhile, a sulfur content of less than 0.01 ppm has a risk of causing difficulty in industrial production of the modified vinyl alcohol-based polymer particles.
- the sulfur content is more preferably 0.1 ppm or more and even more preferably 1 ppm or more.
- the modified vinyl alcohol-based polymer particles thus obtained preferably has a yellow index (YI) measured in accordance with ASTM D1925 of 50 or less.
- YI yellow index
- Use of such a modified vinyl alcohol-based polymer particle allows production of shaped articles, such as films and fiber, with good appearance.
- the modified vinyl alcohol-based polymer particles with a good hue are used as a column filler, it is possible to determine deterioration of a column using a change in hue as an index.
- the YI is more preferably 40 or less, even more preferably 30 or less, and particularly preferably 20 or less.
- Modified vinyl alcohol-based polymer particles of the present invention include a vinyl ester unit represented by a formula (2) below, wherein a vinyl alcohol unit content is from 95 to 99.99 mol % and a sulfur content is from 0.01 to 20000 ppm based on the total constitutional units, and an average particle diameter is from 50 to 2000 ⁇ m:
- X denotes a carbon-carbon bond or a divalent saturated hydrocarbon group having a carbon number from 1 to 10 optionally having a branched structure
- Y denotes a hydrogen atom or a saturated hydrocarbon group having a carbon number from 1 to 6 optionally having a branched structure
- Z denotes a hydrogen atom or a methyl group.
- the vinyl ester unit represented by the formula (2) in the modified vinyl alcohol-based polymer particles of the present invention is the same as the vinyl ester unit represented by the formula (2) in the modified vinyl alcohol-based polymer particles obtained by the production method described above.
- a ratio of three or more consecutive vinyl ester units to the total vinyl ester units is 10 mol % or less in the modified vinyl alcohol-based polymer of the present invention. It is also preferred that a yellow index (YI) of the modified vinyl alcohol-based polymer particles measured in accordance with ASTM D1925 is 50 or less. It is also preferred that a content of the vinyl ester unit represented by the formula (2) based on the total constitutional units in the modified vinyl alcohol-based polymer particles is from 0.01 to 5 mol %.
- the above modified vinyl alcohol-based polymer particles have a low sulfur content, excellent high-energy beam reactivity, and an average particle diameter in a predetermined range, and thus are preferably used as column fillers.
- the modified vinyl alcohol-based polymer particles of the present invention have a good hue, have high viscosity stability when used in the form of an aqueous solution, and causes less odor, and thus are also preferably used for shaped articles, such as films and fiber.
- the modified vinyl alcohol-based polymer particles of the present invention having an average particle diameter in a predetermined range are efficiently transported, and thus cost reduction is expected.
- the modified vinyl alcohol-based polymer particles of the present invention have a low content of fine powder containing sulfur, and thus allow preventing health damage of operators from sucking them.
- a ratio of the three or more consecutive vinyl ester groups based on the total vinyl ester units was calculated in accordance with a formula below from an integral of (a) from 4.7 to 4.9 ppm (central methine proton in hydroxyl group—vinyl ester group—hydroxyl group), (b) from 4.9 to 5.05 ppm (central methine proton in hydroxyl group—vinyl ester group—vinyl ester group), and (c) from 5.05 to 5.25 ppm (central methine proton in three consecutive vinyl ester groups).
- Modified vinyl alcohol-based polymer particles were dispersed in methanol and a volume-average particle diameter ( ⁇ m) was measured using a laser diffractometer “LA-950V2” manufactured by Horiba, Ltd.
- a specific surface area (m 2 /g) of modified vinyl alcohol-based polymer particles was determined by the BET single point method employing nitrogen adsorption.
- the YI (ASTM D1925) of the modified vinyl alcohol-based polymer particles obtained in any of Examples and Comparative Examples was measured using a spectral colorimeter “CM-8500d” manufactured by Konica Minolta, Inc. (using D65 light source, CM-A120 white calibration plate, CM-A126 petri dish set, regular reflection measurement SCE, measurement diameter (p 30 mm). To a petri dish, 5 g of the sample was added and the petri dish was shaken by lightly tapping on a side not to press the powder to uniformly spread the powder. In this state, measurement was performed 10 times in total (remeasured after shaking the petri dish once in each time) to define an average value of them as the YI of the polymer particles.
- CM-8500d manufactured by Konica Minolta, Inc.
- the evaluation film thus obtained was immersed in a boiling water for 1 hour and then taken out of the water. After vacuum drying at 40° C. for 12 hours, a mass (W1) was measured. From the mass (W1) thus obtained and the mass (W2) of the film before immersion, an elution rate under the boiling conditions was calculated in accordance with a formula below, and the elution rate was used as an index of photosensitivity (a lower elution rate indicates higher photosensitivity). It should be noted that, in the case where an evaluation film was dissolved during immersion in water, it was evaluated as “unmeasurable” and indicated with “-” in Table 1.
- a viscosity ⁇ 0 immediately after preparing an aqueous solution (concentration of mass %) in which the particles obtained in any of Examples and Comparative Examples and a viscosity ⁇ 7 7 days after the preparation were respectively measured, followed by calculation of a viscosity ratio ⁇ 7 / ⁇ 0 to evaluate the viscosity stability by criteria below.
- a greater viscosity ratio ⁇ 7 / ⁇ 0 means a greater degree of increase in the viscosity of the solution and poor viscosity stability.
- the modified vinyl alcohol-based polymer particles obtained in any of Examples and Comparative Examples were irradiated with electron beams at 150 kGy to impart water resistance by crosslinking.
- the filtrate was recovered and the point when 90% (i.e., 117 parts by mass) of the added mixture was collected as the filtrate was defined as “completion of filtration” and the liquid flow was evaluated by the time taken from start of filtration to completion of filtration.
- modified vinyl alcohol-based polymer particles obtained in any of Examples and Comparative Examples were dried at 80° C. for 12 hours and then a sulfur content of the modified vinyl alcohol-based polymer particles was measured using an organic element analyzer 240011 manufactured by PerkinElmer, Inc.
- the modified vinyl alcohol-based polymer particles thus obtained, the olefin proton peak derived from the unsaturated hydrocarbon group and the methine proton peak of the vinyl ester group were overlapped, and thus it was not possible to calculate the ratio of the three or more consecutive vinyl ester groups. Then, the modified vinyl alcohol-based polymer particles were dissolved (modified vinyl alcohol-based polymer particle content of 5 mass %) in water, and then 1 mol of propanethiol was added per mol of the olefin, and 1 mol of 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone was further added as a photoinitiator per mol of propanethiol.
- the solution thus prepared was irradiated with ultraviolet rays at an intensity of 3000 mJ/cm 2 .
- the solution thus obtained was added to a large amount of methanol to precipitate polymer particles, and then the particles were analyzed by 1 H-NMR and this time it was possible to calculate the ratio of the three or more consecutive vinyl ester groups because the olefin proton peak was disappeared due to the addition of thiol.
- the mixture was sufficiently stirred and uniformly blended into the entire polyvinyl alcohol resin and then heated, while stirring, to 70° C. and reacted in the state of powder for 5 hours. Then, the powder was washed with a large amount of methanol and then dried at 40° C. and 1.3 Pa for 12 hours to obtain target particles.
- the structural analysis results and the physical property evaluation results of the modified vinyl alcohol-based polymer particles thus obtained are shown in Table 1.
- a reactor provided with a stirrer, a reflux condenser, and an inlet port, 288.0 parts by mass of ion exchange water was charged, and 100 parts by mass of a commercially available polyvinyl alcohol resin (viscosity-average degree of polymerization of 500, degree of saponification of 98.5 mol %, and average particle diameter of 723 ⁇ m) was added while stirring, heated to 95° C., and heated and stirred for 3 hours to obtain a homogeneous solution.
- a commercially available polyvinyl alcohol resin viscosity-average degree of polymerization of 500, degree of saponification of 98.5 mol %, and average particle diameter of 723 ⁇ m
- the solution was cooled to room temperature, and 558.0 parts by mass of methacrylic acid, 2 parts by mass of p-methoxyphenol, and 27.0 parts by mass of a 36% aqueous hydrochloric acid solution were sequentially charged while stirring, heated to 80° C. while stirring, and reacted in the state of a homogeneous solution for 2 hours, and then cooled to room temperature.
- the solution thus obtained was diluted and added in small portions to a large amount of strongly stirred methanol to precipitate the modified vinyl alcohol-based polymer microparticles.
- the precipitate was recovered and further washed with a large amount of methanol, and then dried at 40° C. and 1.3 Pa for 12 hours to obtain target microparticles.
- the structural analysis results and the physical property evaluation results of the modified vinyl alcohol-based polymer particles thus obtained are shown in Table 1.
- the production method of the present invention allows modification without changing the particle shape, and thus allows convenient isolation of the modified vinyl alcohol-based polymer particles without operation of precipitating the reaction product in a poor solvent.
- the modified vinyl alcohol-based polymer particles of the present invention exhibited high viscosity stability and caused less odor due to the sulfur content when used in the form of an aqueous solution.
- the modified vinyl alcohol-based polymer particles also had excellent high-energy beam reactivity and had excellent liquid flow when used as a column filler after crosslinking.
- the production method of the present invention did not use DMSO, it was also possible to suppress contamination of the sulfur content.
- the modified vinyl alcohol-based polymer particles obtained by reacting while the vinyl alcohol-based polymer particles were dissolved had an average particle diameter of less than 50 ⁇ m and had poor liquid flow.
- use of DMSO during the reaction caused an extremely large content of sulfur in the modified vinyl alcohol-based polymer particles.
- the modified vinyl alcohol-based polymer particles obtained in Example 6 was subjected to evaluation as a column filler.
- the particles were irradiated with electron beams at 150 kGy for impartation of water resistance by crosslinking.
- a chromatographic column (having a glass filter with an inner diameter of 50 mm and an opening diameter from 40 to 50 ⁇ m and a stopcock) was filled with 100 parts by mass of the modified vinyl alcohol-based polymer particles thus crosslinked and 1000 parts by mass of super dehydrated methanol was flown as an eluate to wet the polymer particles.
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Abstract
A method of producing modified vinyl alcohol-based polymer particles, includes mixing vinyl alcohol-based polymer particles with a mixed medium containing unsaturated carboxylic acid, an acid catalyst, and water, wherein, by mixing the vinyl alcohol-based polymer particles with the mixed medium, the vinyl alcohol-based polymer particles are reacted with the unsaturated carboxylic acid to obtain modified vinyl alcohol-based polymer particles containing a vinyl ester unit represented by a formula (2) below, having a vinyl alcohol unit content based on the total constitutional units from 95 to 99.99 mol %, and having an average particle diameter from 50 to 2000 μm. The production method does not cause the problem of the residual sulfur content derived from a liquid medium used for reaction and is also capable of modifying the vinyl alcohol-based polymer particles while maintaining the particle shape.
Description
- The present invention relates to a method of producing modified vinyl alcohol-based polymer particles having an unsaturated hydrocarbon group in a side chain and to particles obtained by the same.
- Vinyl alcohol-based polymers represented by polyvinyl alcohol have excellent interfacial properties and strength properties as those of a limited number of crystalline water-soluble polymers, and thus are used for paper processing, fiber processing, emulsion stabilizers, and the like. Vinyl alcohol-based polymer gels obtained by crosslinking such a vinyl alcohol-based polymer by various methods are used for, due to their hydrophilicity and safety, super absorbent polymers, contact lenses, aqueous/organic solvent-based SEC column fillers, and the like. In particular, vinyl alcohol-based polymers having a vinyl alcohol unit content of 95 mol % or more exhibit high hydrophilicity as column fillers, and films and fiber obtained using an aqueous solution of such a vinyl alcohol-based polymer have excellent strength. To improve specific functions, attempts are made to introduce a functional group and the like into the vinyl alcohol-based polymer and various modified vinyl alcohol-based copolymers are developed.
- Among all, modified vinyl alcohol-based polymers having an unsaturated hydrocarbon group introduced into a side chain may be subjected to impartation of water resistance by crosslinking by high-energy beam radiation, modification by graft polymerization, and the like. As a method of introducing an unsaturated hydrocarbon group into a side chain, a generally used method causes the hydroxyl group in the vinyl alcohol-based polymer to be reacted with various compounds. For example, Patent Document 1 discloses a method of synthesizing a vinyl alcohol-based polymer containing an unsaturated hydrocarbon group by acetalization using aldehyde having an unsaturated hydrocarbon group. Patent Document 2 discloses a method of synthesizing a vinyl alcohol-based polymer containing an unsaturated hydrocarbon group by etherification using an epoxy compound having an unsaturated hydrocarbon group. However, some among compounds such as aldehyde and epoxy are considered to have mutagenicity and there is a demand for a method not using these compounds.
- Meanwhile, there are disclosed methods of synthesizing a vinyl alcohol-based polymer containing an unsaturated hydrocarbon group by esterification using the safer unsaturated carboxylic acid or unsaturated carboxylic ester. For example, Patent Documents 3 and 4 disclose methods of obtaining a modified vinyl alcohol-based polymer comprising: dissolving a vinyl alcohol-based polymer in dimethyl sulfoxide (DMSO), followed by transesterification with unsaturated carboxylic ester; and then precipitation in a poor solvent. Patent Document 5 describes a method comprising: dissolving a vinyl alcohol-based polymer in water; and then esterifying with unsaturated carboxylic acid and an acid catalyst to produce a solution containing a modified vinyl alcohol-based polymer. Non-Patent Document 1 discloses a method of obtaining a modified vinyl alcohol-based polymer comprising: dissolving a vinyl alcohol-based polymer in water; followed by esterification with unsaturated carboxylic acid, acetic acid, and an acid catalyst; and then precipitation in a poor solvent.
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- Patent Document 1: JP 2009-108305 A
- Patent Document 2: JP 2003-231715 A
- Patent Document 3: WO 2018/124015
- Patent Document 4: WO 2018/124014
- Patent Document 5: JP 2007-321099 A
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- Non-Patent Document 1: Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 35, 3603-3611 (1997)
- However, in the methods of producing a modified vinyl alcohol-based polymer described in Patent Documents 3 and 4, transesterification is carried out in a state where the vinyl alcohol-based polymer is dissolved in DMSO. To isolate the modified vinyl alcohol-based polymer, the polymer thus has to be precipitated in a large amount of poor solvent after the transesterification, causing extreme complication and economic disadvantages. In the case of precipitating a polymer by such a method, it is difficult to control the shape of particles and it is also found that use of the polymer thus obtained as a column filler causes problems of poor liquid flow and the like.
- The present inventors also find a problem that, having extremely high affinity for vinyl alcohol-based polymers, DMSO is likely to remain in the resin even when precipitated in a poor solvent. Thus, use of the vinyl alcohol-based polymer thus obtained as a column filler has a problem that the sulfur content is eluted over time to cause contamination. In addition, there is also a problem of strong odor due to the residual sulfur content while the modified vinyl alcohol-based polymer obtained by either production method described in Patent Documents 3 or 4 is stored in the form of an aqueous solution.
- Use water, not DMSO as the solvent for esterification, the methods of producing a modified vinyl alcohol-based polymer described in Patent Document 5 and Non-Patent Document 1 can solve the problem of the residual sulfur content while, to isolate the modified vinyl alcohol-based polymer, the polymer has to be precipitated in a large amount of poor solvent after esterification, causing extreme complication and economic disadvantages. In the case of precipitating a polymer by such a method, it is difficult to control the shape of particles and it is also found that use of the polymer thus obtained as a column filler causes problems of poor liquid flow and the like. Moreover, Patent Document 5 only discloses the solution containing a modified vinyl alcohol-based polymer and does not disclose the particle shape at all.
- The present invention has been made to solve the above problems, and it is an object thereof to provide a method of producing modified vinyl alcohol-based polymer particles having an unsaturated hydrocarbon group that is capable of controlling the particle shape and has excellent cost efficiency. It is also an object thereof to provide modified vinyl alcohol-based polymer particles having an unsaturated hydrocarbon group that have a low sulfur content, and have an average particle diameter in a predetermined range.
- The present inventors have been studied intensively to solve the above problems, and as a result, they have found the following. That is, that reaction of unsaturated carboxylic acid with vinyl alcohol-based polymer particles by mixing vinyl alcohol-based polymer particles with a mixed medium containing unsaturated carboxylic acid, an acid catalyst, and water allows not only omitting precipitation in a large amount of poor solvent for isolation of the reaction product but also controlling the particle shape of the modified vinyl alcohol-based polymer to be obtained. They have also found that reduction in the sulfur content reduces the odor while the modified vinyl alcohol-based polymer particles are used in the form of an aqueous solution. Moreover, they have found that the modified vinyl alcohol-based polymer particles having an average particle diameter in a specific range and also having a reduced sulfur content allow the problems of liquid flowability and contamination to be solved when the modified vinyl alcohol-based polymer particles are used as a column filler, and thus have come to complete the present invention.
- That is, the above problems are solved by providing a method of producing modified vinyl alcohol-based polymer particles, comprising mixing vinyl alcohol-based polymer particles with a mixed medium containing unsaturated carboxylic acid, an acid catalyst, and water, wherein
- the unsaturated carboxylic acid is represented by a formula (1) below, and,
- by mixing the vinyl alcohol-based polymer particles with the mixed medium, the vinyl alcohol-based polymer particles are reacted with the unsaturated carboxylic acid to obtain modified vinyl alcohol-based polymer particles containing a vinyl ester unit represented by a formula (2) below, having a vinyl alcohol unit content based on the total constitutional units from 95 to 99.99 mol %, and having an average particle diameter from 50 to 2000 μm,
- [in the formula (1), X denotes a carbon-carbon bond or a divalent saturated hydrocarbon group having a carbon number from 1 to 10 optionally having a branched structure, Y denotes a hydrogen atom or a saturated hydrocarbon group having a carbon number from 1 to 6 optionally having a branched structure, and Z denotes a hydrogen atom or a methyl group,]
- [in the formula (2), X, Y, and Z denote the same as in the formula (1).]
- In this context, it is preferred that the modified vinyl alcohol-based polymer particles have a specific surface area from 0.01 to 1.0 m2/g. It is also preferred that the mixed medium has a water content from 1 to 30 mass %. It is also preferred that the mixed medium further contains acetic acid. It is also preferred that Y denotes a hydrogen atom. It is also preferred that X denotes a carbon-carbon bond.
- The production method preferably further comprises washing the modified vinyl alcohol-based polymer particles.
- The above problems are also solved by providing modified vinyl alcohol-based polymer particles comprising a vinyl ester unit represented by a formula (2) below, wherein a vinyl alcohol unit content is from 95 to 99.99 mol % and a sulfur content is from 0.01 to 20000 ppm based on the total constitutional units, and an average particle diameter is from 50 to 2000 μm:
- [in the formula (2), X denotes a carbon-carbon bond or a divalent saturated hydrocarbon group having a carbon number from 1 to 10 optionally having a branched structure, Y denotes a hydrogen atom or a saturated hydrocarbon group having a carbon number from 1 to 6 optionally having a branched structure, and Z denotes a hydrogen atom or a methyl group.]
- In this context, it is preferred that a ratio of three or more consecutive vinyl ester units to the total vinyl ester units is 10 mol % or less in the modified vinyl alcohol-based polymer. It is also preferred that a yellow index (YI) of the modified vinyl alcohol-based polymer particles measured in accordance with ASTM D1925 is 50 or less. It is also preferred that a content of the vinyl ester unit represented by the formula (2) based on the total constitutional units in the modified vinyl alcohol-based polymer particles is from 0.01 to 5 mol %. It is also preferred that Y denotes a hydrogen atom. It is also preferred that X denotes a carbon-carbon bond.
- The method of producing modified vinyl alcohol-based polymer particles of the present invention does not cause the problem of the residual sulfur content derived from a liquid medium used for reaction and the like and is also capable of modifying the vinyl alcohol-based polymer particles while maintaining the particle shape, and thus the method needs no process for precipitating the polymer in a large amount of poor solvent, thereby being convenient and economically excellent. The modified vinyl alcohol-based polymer particles of the present invention have a low sulfur content, have excellent high-energy beam reactivity, and have an average particle diameter in a predetermined range, and thus are preferably used for a column filler and the like. Moreover, the modified vinyl alcohol-based polymer particles cause less odor for production of films and fiber while the particles are used in the form of an aqueous solution.
- The present invention is a method of producing modified vinyl alcohol-based polymer particles, comprising mixing vinyl alcohol-based polymer particles with a mixed medium containing unsaturated carboxylic acid, an acid catalyst, and water, wherein
- the unsaturated carboxylic acid is represented by a formula (1) below, and,
- by mixing the vinyl alcohol-based polymer particles with the mixed medium, the vinyl alcohol-based polymer particles are reacted with the unsaturated carboxylic acid to obtain modified vinyl alcohol-based polymer particles containing a vinyl ester unit represented by a formula (2) below, having a vinyl alcohol unit content based on the total constitutional units from 95 to 99.99 mol %, and having an average particle diameter from 50 to 2000 μm,
- [in the formula (1), X denotes a carbon-carbon bond or a divalent saturated hydrocarbon group having a carbon number from 1 to 10 optionally having a branched structure, Y denotes a hydrogen atom or a saturated hydrocarbon group having a carbon number from 1 to 6 optionally having a branched structure, and Z denotes a hydrogen atom or a methyl group,]
- [in the formula (2), X, Y, and Z denote the same as in the formula (1).]
- In the production method of the present invention, as unsaturated carboxylic acid to be reacted with the vinyl alcohol-based polymer particles, one that is represented by the formula (1) is used. X in the formula (1) denotes a carbon-carbon bond or a divalent saturated hydrocarbon group having a carbon number from 1 to 10 optionally having a branched structure. From the perspective of high-energy beam reactivity, it is preferred that X denotes a carbon-carbon bond. Specific examples of the unsaturated carboxylic acid when X denotes a carbon-carbon bond include methacrylic acid, acrylic acid, crotonic acid, and the like.
- The saturated hydrocarbon group used as X has a carbon number from 1 to 10. The carbon number of more than 10 causes worsening of water solubility. The carbon number is preferably 5 or less, more preferably 3 or less, and even more preferably 2 or less.
- Examples of the divalent saturated hydrocarbon group used as X include alkylene groups, cycloalkylene groups, and the like. Examples of the alkylene groups include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, and the like. Examples of the cycloalkylene groups include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and the like. The alkylene groups and the cycloalkylene groups used as X optionally have an alkyl group, such as a methyl group and an ethyl group, as the branched structure.
- Y in the formula (1) denotes a hydrogen atom or a saturated hydrocarbon group having a carbon number from 1 to 6 optionally having a branched structure. It is preferred that Y denotes a hydrogen atom.
- The saturated hydrocarbon group used as Y has a carbon number from 1 to 6. The carbon number of more than 6 has a risk of causing worsening of water solubility. The carbon number is preferably 5 or less, more preferably 3 or less, and even more preferably 2 or less.
- Examples of the saturated hydrocarbon group used as Y include alkyl groups, cycloalkyl groups, and the like. Examples of the alkyl groups include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, and the like. Examples of the cycloalkyl groups include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like. The alkyl groups and the cycloalkyl groups used as Y optionally have an alkyl group, such as a methyl group and an ethyl group, as the branched structure.
- Specific examples of the unsaturated carboxylic acid represented by the formula (1) include methacrylic acid, acrylic acid, crotonic acid, 3-methyl-3-butenoic acid, 4-pentenoic acid, 2-methyl-4-pentenoic acid, 5-hexenoic acid, 3,3-dimethyl-4-pentenoic acid, 7-octenoic acid, trans-3-pentenoic acid, trans-4-decenoic acid, 10-undecenoic acid, and the like. Among all, from the perspective of industrial availability and reactivity, methacrylic acid, acrylic acid, 4-pentenoic acid, and 10-undecenoic acid are preferred.
- In the production method of the present invention, an acid catalyst is used as the catalyst for reaction of vinyl alcohol-based polymer particles with the unsaturated carboxylic acid. This accelerates the reaction of the vinyl alcohol-based polymer particles with the unsaturated carboxylic acid. The acid catalyst may catalyze dehydration esterification of the unsaturated carboxylic acid represented by the formula (1) and the hydroxyl groups in the vinyl alcohol-based polymer particles, and either of organic acid and inorganic acid may be used. Examples of the organic acid include methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and paratoluenesulfonic acid. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, and nitric acid. Among all, methanesulfonic acid, paratoluenesulfonic acid, and sulfuric acid are preferred, and paratoluenesulfonic acid is particularly preferred.
- The vinyl alcohol-based polymer constituting the vinyl alcohol-based polymer particles used in the present invention preferably has a degree of saponification from 95 to 99.99 mol %. The vinyl alcohol-based polymer preferably has a viscosity-average degree of polymerization from 100 to 5000 and more preferably from 200 to 4000. A viscosity-average degree of polymerization of less than 100 has a risk of reducing the mechanical strength of a modified vinyl alcohol-based polymer to be obtained. Meanwhile, a viscosity-average degree of polymerization of more than 5000 has a risk of causing difficulty in industrial production of the vinyl alcohol-based polymer particles. The degree of saponification and the viscosity-average degree of polymerization of the vinyl alcohol-based polymer are measured in accordance with JIS K6726.
- The vinyl alcohol units in the vinyl alcohol-based polymer may be derived from vinyl ester units by hydrolysis, alcoholysis, and the like. Accordingly, depending on the conditions for conversion from vinyl ester units to vinyl alcohol units and the like, vinyl ester units sometimes remain in the vinyl alcohol-based polymer.
- Examples of vinyl ester of the vinyl ester units include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate, vinyl benzoate, and the like. Among them, vinyl acetate is preferred from an industrial perspective.
- Without inhibiting the effects of the present invention, the vinyl alcohol-based polymer may contain vinyl alcohol units and monomer units other than the vinyl ester units. Examples of such another monomer unit include those derived from ethylenic unsaturated monomers copolymerizable with vinyl ester. Examples of such an ethylenic unsaturated monomer include: α-olefins, such as ethylene, propylene, n-butene, isobutylene, and 1-hexene, acrylic acid and salts thereof; acrylic esters, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, and octadecyl acrylate; methacrylic acid and salts thereof; methacrylic esters, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, and octadecyl methacrylate; acrylamide, N-methylacrylamide, N-ethylacrylamide, N,N-dimethylacrylamide, diacetone acrylamide, acrylamidopropanesulfonic acid and salts thereof, acrylamide propyldimethylamine and salts thereof (e.g., quaternary salts); methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, methacrylamidopropanesulfonic acid and salts thereof, methacrylamide propyldimethylamine and salts thereof (e.g., quaternary salts); vinyl ethers, such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether, and 2,3-diacetoxy-1-vinyloxypropane; vinyl cyanides, such as acrylonitrile and methacrylonitrile; vinyl halides, such as vinyl chloride and vinyl fluoride; vinylidene halides, such as vinylidene chloride and vinylidene fluoride; allyl compounds, such as allyl acetate, 2,3-diacetoxy-1-allyloxypropane, and allyl chloride; unsaturated dicarboxylic acids, such as maleic acid, itaconic acid, and fumaric acid, and salts thereof and esters thereof; vinylsilyl compounds, such as vinyltrimethoxysilane; isopropenyl acetate; and the like.
- The contents of the vinyl alcohol units and the monomer units other than the vinyl ester units in the vinyl alcohol-based polymer is usually 10 mol % or less, preferably 5 mol % or less, and more preferably 1 mol % or less.
- The vinyl alcohol-based polymer particles used in the present invention preferably has an average particle diameter from 50 to 2000 μm. An average particle diameter of less than 50 μm has a risk of causing insufficient liquid flow when modified vinyl alcohol-based polymer particles thus obtained are used as a column filler. The average particle diameter is more preferably 100 μm or more, even more preferably 200 μm or more, particularly preferably 300 μm or more, and most preferably 500 μm or more. Meanwhile, an average particle diameter of more than 2000 μm, there is a risk that reaction does not uniformly proceed inside and outside the particles. The average particle diameter is more preferably 900 μm or less and even more preferably 800 μm or less.
- By mixing the vinyl alcohol-based polymer particles with a mixed medium containing the unsaturated carboxylic acid represented by the formula (1), the acid catalyst, and water, the vinyl alcohol-based polymer particles are reacted with the unsaturated carboxylic acid to obtain modified vinyl alcohol-based polymer particles. The vinyl alcohol-based polymer particles are thus reacted with the unsaturated carboxylic acid, that is, reaction is carried out while maintaining the particle shape of the vinyl alcohol-based polymer particles as a raw material, thereby allowing not only omitting precipitation in a large amount of poor solvent for isolation of the reaction product but also controlling the particle shape of the modified vinyl alcohol-based polymer particles. In addition, there is no problem that a sulfur content derived from a liquid medium used for reaction and the like remains in the modified vinyl alcohol-based polymer particles. Further, in the modified vinyl alcohol-based polymer particles thus obtained, a ratio of three or more consecutive vinyl ester units is reduced and thus viscosity stability used in the form of an aqueous solution is improved. As a method of reacting the vinyl alcohol-based polymer particles with the unsaturated carboxylic acid, a preferred method comprises: mixing the vinyl alcohol-based polymer particles with the mixed medium; thereby dispersing the vinyl alcohol-based polymer particles in the mixed medium to react the vinyl alcohol-based polymer particles with the unsaturated carboxylic acid. A specific example includes a method comprising: mixing the vinyl alcohol-based polymer particles with the mixed medium to form a slurry or a dispersion; thereby reacting the vinyl alcohol-based polymer particles with the unsaturated carboxylic acid. Other examples include a method comprising: uniformly blending the vinyl alcohol-based polymer particles with the mixed medium; thereby reacting the vinyl alcohol-based polymer particles with the unsaturated carboxylic acid, and the like.
- A method of mixing the vinyl alcohol-based polymer particles with the mixed medium is not particularly limited as long as it is capable of uniformly mixing both. Specific examples include (1) a method comprising: preparing the mixed medium; and then mixing the vinyl alcohol-based polymer particles with the mixed medium, (2) a method comprising: mixing the vinyl alcohol-based polymer with some components of the mixed medium; and then mixing a mixture thus obtained with the rest of the components of the mixed medium, (3) a method comprising: simultaneously mixing each component of the mixed medium with the vinyl alcohol-based polymer particles, and the like, and among all, (1) is preferred.
- A mass ratio [polymer particles/mixed medium] of the vinyl alcohol-based polymer particles to the mixed medium for mixing the vinyl alcohol-based polymer particles with the mixed medium is preferably from 3/97 to 90/10. A mass ratio [polymer particles/mixed medium] of less than 3/97 has a risk of severely reducing the reactivity. The mass ratio [polymer particles/mixed medium] is more preferably 10/90 or more. Meanwhile, a mass ratio [polymer particles/mixed medium] of more than 90/10 has a risk of not allowing uniform mixing of the vinyl alcohol-based polymer particles with the mixed medium and a risk of severely reducing the reactivity. The mass ratio [polymer particles/mixed medium] is more preferably 80/20 or less and even more preferably 50/50 or less.
- A water content in the mixed medium is preferably from 1 to 30 mass %. A water content of less than 1 mass % has a risk that the modified vinyl alcohol-based polymer particles to be obtained is likely to be colored. The water content is more preferably 3 mass % or more, even more preferably 5 mass % or more, and particularly preferably 8 mass % or more. Meanwhile, a water content of more than 30 mass % has a risk of dissolving the vinyl alcohol-based polymer during reaction, causing difficulty in modification of the vinyl alcohol-based polymer particles while maintaining the particle shape. The water content is more preferably 20 mass % or less and even more preferably 18 mass % or less.
- For reaction of the vinyl alcohol-based polymer particles with the unsaturated carboxylic acid, an amount of the acid catalyst to be added is preferably from 0.0001 to 0.1 mol per mol of hydroxyl group in the vinyl alcohol-based polymer. The amount to be added is more preferably 0.0005 mol or more. Meanwhile, the amount to be added is more preferably 0.08 mol or less.
- A content of the unsaturated carboxylic acid in the mixed medium is preferably from 5 to 2000 parts by mass based on 100 parts by mass of the vinyl alcohol-based polymer particles. An amount of the unsaturated carboxylic acid to be added of less than 5 parts by mass has a risk of reducing the reactivity. The content of the unsaturated carboxylic acid is more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, and particularly preferably 30 parts by mass or more. Meanwhile, a content of the unsaturated carboxylic acid of more than 2000 parts by mass has a risk of increasing unreacted unsaturated carboxylic acid and increasing the costs. The content of the unsaturated carboxylic acid is more preferably 1500 parts by mass or less, even more preferably 1000 parts by mass or less, and particularly preferably 700 parts by mass or less.
- From the perspective of controlling a content of vinyl acetate units in the modified vinyl alcohol-based polymer, the mixed medium preferably further contains acetic acid. A content of the acetic acid in the mixed medium is preferably from 1 to 1000 parts by mass based on 100 parts by mass of water in the mixed medium. The content of the acetic acid is more preferably 5 parts by mass or more and even more preferably 10 parts by mass or more. Meanwhile, the content of the acetic acid is more preferably 800 parts by mass or less and even more preferably 600 parts by mass or less.
- The mixed medium may contain additives other than the unsaturated carboxylic acid represented by the formula (1), the acid catalyst, water, and acetic acid. Examples of such an additive include surfactants and organic solvents. Examples of the surfactant include: nonionic surfactants, such as polyoxyethylene-alkyl ether type, polyoxyethylene-alkyl phenol type, polyoxyethylene-polyhydric alcohol ester type, esters of polyhydric alcohol and fatty acid, and oxyethylene-oxypropylene block polymers; anionic surfactants, such as higher alcohol sulfate, alkali salt of higher fatty acid, polyoxyethylene alkylphenol ether sulfate, alkylbenzene sulfonate, naphthalene sulfonate formalin condensate, alkyl diphenyl ether sulfonate, dialkyl sulfosuccinate, and higher alcohol phosphate salt; and reactive surfactants. Examples of the organic solvent include: alcohols, such as methanol, ethanol, propanol, and butanol; aliphatic or alicyclic hydrocarbons, such as n-hexane, n-pentane, and cyclohexane; aromatic hydrocarbons, such as benzene and toluene; nitriles, such as acetonitrile and benzonitrile; ethers, such as diethyl ether, diphenyl ether, anisole, 1,2-dimethoxyethane, and 1,4-dioxane; ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone, and methyl isobutyl ketone; esters, such as methyl acetate, ethyl acetate, and ethyl propionate; and the like. Examples of such another additive also include ultraviolet absorbers, light stabilizers, antioxidants, plasticizers, and defoamers. The content of these other additives in the mixed medium is preferably 50 mass % or less and more preferably 35 mass % or less. The mixed medium preferably does not contain a liquid medium containing sulfur.
- A temperature for reacting the vinyl alcohol-based polymer particles with the unsaturated carboxylic acid is preferably from 10° C. to 120° C. The temperature is more preferably 30° C. or more and even more preferably 50° C. or more. Meanwhile, the temperature is more preferably 100° C. or less and even more preferably 90° C. or less. Reaction time for reacting the vinyl alcohol-based polymer particles with the unsaturated carboxylic acid is usually from 0.5 to 72 hours.
- It is preferred to further wash the modified vinyl alcohol-based polymer particles after reaction. Examples of the specific washing method include a method comprising washing the particles with a solvent. Specific examples include a method comprising: immersing the particles in a solvent; and then draining, a method comprising circulating a solvent in a washing column while contacting the particles with the solvent for washing, a method comprising flowing the particles while spraying a washing solvent, and the like. Examples of the solvent to be used include: alcohols, such as methanol, ethanol, propanol, and butanol; aliphatic and alicyclic hydrocarbons, such as n-hexane, n-pentane, and cyclohexane; aromatic hydrocarbons, such as benzene and toluene; nitriles, such as acetonitrile and benzonitrile; ethers, such as diethyl ether, diphenyl ether, anisole, 1,2-dimethoxyethane, and 1,4-dioxane; ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone, and methyl isobutyl ketone; esters, such as methyl acetate, ethyl acetate, and ethyl propionate; and the like. Among all, alcohols, ethers, ketones, and esters are more preferred, methanol, ethanol, propanol, diethyl ether, 1,2-dimethoxyethane, acetone, methyl ethyl ketone, methyl acetate, and ethyl acetate are even more preferred, and methanol, propanol, acetone, methyl ethyl ketone, methyl acetate, and ethyl acetate are particularly preferred. One type of these organic solvents may be used singly or two or more types of them may be used together.
- It is preferred to wash the modified vinyl alcohol-based polymer particles after reaction as needed and then to dry the particles. In this situation, usually, the drying temperature is from 20° C. to 150° C. and the drying time is from 1 to 72 hours. The modified vinyl alcohol-based polymer particles may be dried under atmospheric pressures or under reduced pressures.
- The modified vinyl alcohol-based polymer particles thus obtained have to have an average particle diameter from 50 to 2000 μm. The modified vinyl alcohol-based polymer particles having such an average particle diameter are excellent in liquid flowability and the like when used as a column filler. The production method of the present invention facilitates controlling the particle shape of the modified vinyl alcohol-based polymer and thus allows convenient production of the modified vinyl alcohol-based polymer particles having such an average particle diameter. An average particle diameter of less than 50 μm causes insufficient liquid flow when the modified vinyl alcohol-based polymer particles thus obtained are used as a column filler. The average particle diameter is preferably 100 μm or more, more preferably 200 μm or more, even more preferably 300 μm or more, and particularly preferably 500 μm or more. Meanwhile, an average particle diameter of more than 2000 μm causes reaction not to uniformly proceed inside and outside the particles during production of the modified vinyl alcohol-based polymer particles. The average particle diameter is preferably 900 μm or less and more preferably 800 μm or less.
- It is preferred that the modified vinyl alcohol-based polymer particles obtained have a specific surface area from 0.01 to 1.0 m2/g. A specific surface area of less than 0.01 m2/g has a risk of worsening separation performance when used as a column filler. The specific surface area is more preferably 0.1 m2/g or more. Meanwhile, a specific surface area of more than 1.0 m2/g has a risk of causing consolidation of the particles and poor filtration when used as a column filler.
- From the perspective of improving the viscosity stability used in the form of an aqueous solution, the modified vinyl alcohol-based polymer particles thus obtained preferably has a ratio of three or more consecutive vinyl ester units to the total vinyl ester units of 10 mol % or less. The ratio is more preferably 9 mol % or less, even more preferably 8 mol % or less, and particularly preferably 7 mol % or less. Meanwhile, the ratio of three or more consecutive vinyl ester units is usually 0.1 mol % or more. It is possible to obtain the ratio of three or more consecutive vinyl ester units by a method using 1H-NMR measurement described later in Examples.
- The modified vinyl alcohol-based polymer thus obtained has to have a vinyl alcohol unit content based on the total constitutional units from 95 to 99.99 mol %. A vinyl alcohol unit content of less than 95 mol % has a risk of severely reducing the crystallinity of the modified vinyl alcohol-based polymer and reducing the mechanical strength. The vinyl alcohol unit content is more preferably 95.5 mol % or more. Meanwhile, a vinyl alcohol unit content of more than 99.99 mol % has a risk of causing difficulty in industrial production of the modified vinyl alcohol-based polymer. The vinyl alcohol unit content is preferably 99.9 mol % or less.
- The modified vinyl alcohol-based polymer particles thus obtained preferably has a content of a vinyl ester unit represented by the formula (2) from 0.01 to 5 mol % based on the total constitutional units. A content of the vinyl ester units of less than 0.01 mol % has a risk that crosslinking reaction does not sufficiently proceed during crosslinking reaction of the modified vinyl alcohol-based polymer particles. The content of the vinyl ester units is more preferably 0.05 mol % or more, even more preferably 0.3 mol % or more, and particularly preferably 0.5 mol % or more. Meanwhile, a content of the vinyl ester units of more than 5 mol % has a risk of causing worsening of water solubility of the modified vinyl alcohol-based polymer particles. It is possible to obtain the content of the vinyl ester unit represented by the formula (2) by a method using 1H-NMR measurement described later in Examples.
- Without inhibiting the effects of the present invention, the modified vinyl alcohol-based polymer particles thus obtained may contain vinyl alcohol units and monomer units other than the vinyl ester units. Examples of such another monomer unit include those described above as the monomer units other than vinyl alcohol units and vinyl ester units contained in the vinyl alcohol-based polymer particles used for production of the modified vinyl alcohol-based polymer particles. The content of the monomer units other than the vinyl alcohol units and the vinyl ester units in the modified vinyl alcohol-based polymer particles is usually 10 mol % or less, preferably 5 mol % or less, and more preferably 1 mol % or less.
- The modified vinyl alcohol-based polymer particles thus obtained preferably has a viscosity-average degree of polymerization from 100 to 5000 and more preferably from 200 to 4000. A viscosity-average degree of polymerization of less than 100 has a risk of reducing the mechanical strength of the modified vinyl alcohol-based polymer particles thus obtained. Meanwhile, a viscosity-average degree of polymerization of more than 5000 has a risk of causing difficulty in industrial production of the vinyl alcohol-based polymer particles. The viscosity-average degree of polymerization of the modified vinyl alcohol-based polymer particles is measured in accordance with JIS K6726.
- The sulfur content in the modified vinyl alcohol-based polymer particles thus obtained is preferably from 0.01 to 20000 ppm. The modified vinyl alcohol-based polymer particles having such a low sulfur content is less likely to cause a problem of contamination due to elution of the sulfur content when used as a column filler. The modified vinyl alcohol-based polymer particles also cause less odor when used in the form of an aqueous solution. The sulfur content is more preferably 10000 ppm or less, even more preferably 5000 ppm or less, and particularly preferably 3000 ppm or less. Meanwhile, a sulfur content of less than 0.01 ppm has a risk of causing difficulty in industrial production of the modified vinyl alcohol-based polymer particles. The sulfur content is more preferably 0.1 ppm or more and even more preferably 1 ppm or more.
- The modified vinyl alcohol-based polymer particles thus obtained preferably has a yellow index (YI) measured in accordance with ASTM D1925 of 50 or less. Use of such a modified vinyl alcohol-based polymer particle allows production of shaped articles, such as films and fiber, with good appearance. When the modified vinyl alcohol-based polymer particles with a good hue are used as a column filler, it is possible to determine deterioration of a column using a change in hue as an index. The YI is more preferably 40 or less, even more preferably 30 or less, and particularly preferably 20 or less.
- Modified vinyl alcohol-based polymer particles of the present invention include a vinyl ester unit represented by a formula (2) below, wherein a vinyl alcohol unit content is from 95 to 99.99 mol % and a sulfur content is from 0.01 to 20000 ppm based on the total constitutional units, and an average particle diameter is from 50 to 2000 μm:
- [in the formula (2), X denotes a carbon-carbon bond or a divalent saturated hydrocarbon group having a carbon number from 1 to 10 optionally having a branched structure, Y denotes a hydrogen atom or a saturated hydrocarbon group having a carbon number from 1 to 6 optionally having a branched structure, and Z denotes a hydrogen atom or a methyl group.]
- The vinyl ester unit represented by the formula (2) in the modified vinyl alcohol-based polymer particles of the present invention is the same as the vinyl ester unit represented by the formula (2) in the modified vinyl alcohol-based polymer particles obtained by the production method described above.
- It is preferred that a ratio of three or more consecutive vinyl ester units to the total vinyl ester units is 10 mol % or less in the modified vinyl alcohol-based polymer of the present invention. It is also preferred that a yellow index (YI) of the modified vinyl alcohol-based polymer particles measured in accordance with ASTM D1925 is 50 or less. It is also preferred that a content of the vinyl ester unit represented by the formula (2) based on the total constitutional units in the modified vinyl alcohol-based polymer particles is from 0.01 to 5 mol %.
- The above modified vinyl alcohol-based polymer particles have a low sulfur content, excellent high-energy beam reactivity, and an average particle diameter in a predetermined range, and thus are preferably used as column fillers. The modified vinyl alcohol-based polymer particles of the present invention have a good hue, have high viscosity stability when used in the form of an aqueous solution, and causes less odor, and thus are also preferably used for shaped articles, such as films and fiber. The modified vinyl alcohol-based polymer particles of the present invention having an average particle diameter in a predetermined range are efficiently transported, and thus cost reduction is expected. In addition, the modified vinyl alcohol-based polymer particles of the present invention have a low content of fine powder containing sulfur, and thus allow preventing health damage of operators from sucking them.
- Although the present invention is described in more detail below with reference to Examples, the present invention is not at all limited by Examples below. It should be noted that “%” and “parts” in Examples and Comparative Examples respectively indicate “mass %” and “parts by mass” unless otherwise specified.
- Using a nuclear magnetic resonance apparatus “LAMBDA 500” manufactured by JEOL Ltd., 1H-NMR of modified vinyl alcohol-based polymer particles was measured at room temperature with a DMSO-d6 solvent, and the vinyl alcohol unit content of the polymer particles was calculated from an integral of a peak (from 3.4 to 4.0 ppm) derived from methine protons bonded to the hydroxyl groups and an integral of a peak (from 4.7 to 5.3 ppm) derived from methine protons of the vinyl ester groups.
- Using a nuclear magnetic resonance apparatus “LAMBDA 500” manufactured by JEOL Ltd., 1H-NMR of modified vinyl alcohol-based polymer particles was measured at room temperature, and a degree of modification of the polymer particles [content (mol %) of the vinyl ester unit represented by the formula (2) based on the total constitutional units] was calculated from an integral of a peak (from 5.0 to 7.5 ppm) derived from olefin protons. For example, in Example 1, the degree of modification was calculated from an integral of the peak derived from olefin protons appearing at 5.6 ppm and 6.0 ppm.
- Using a nuclear magnetic resonance apparatus “LAMBDA 500” manufactured by JEOL Ltd., 1H-NMR of modified vinyl alcohol-based polymer particles was measured at 80° C. with a DMSO-d6 solvent. A ratio of the three or more consecutive vinyl ester groups based on the total vinyl ester units was calculated in accordance with a formula below from an integral of (a) from 4.7 to 4.9 ppm (central methine proton in hydroxyl group—vinyl ester group—hydroxyl group), (b) from 4.9 to 5.05 ppm (central methine proton in hydroxyl group—vinyl ester group—vinyl ester group), and (c) from 5.05 to 5.25 ppm (central methine proton in three consecutive vinyl ester groups).
-
Ratio of Three or more Consecutive Vinyl Ester Groups (%)=(c)/{(a)+(b)+(c)}×100 - Modified vinyl alcohol-based polymer particles were dispersed in methanol and a volume-average particle diameter (μm) was measured using a laser diffractometer “LA-950V2” manufactured by Horiba, Ltd.
- Using a specific surface area measurement apparatus “MONOSORB” manufactured by Yuasa Ionics Co., Ltd., a specific surface area (m2/g) of modified vinyl alcohol-based polymer particles was determined by the BET single point method employing nitrogen adsorption.
- The YI (ASTM D1925) of the modified vinyl alcohol-based polymer particles obtained in any of Examples and Comparative Examples was measured using a spectral colorimeter “CM-8500d” manufactured by Konica Minolta, Inc. (using D65 light source, CM-A120 white calibration plate, CM-A126 petri dish set, regular reflection measurement SCE, measurement diameter (p 30 mm). To a petri dish, 5 g of the sample was added and the petri dish was shaken by lightly tapping on a side not to press the powder to uniformly spread the powder. In this state, measurement was performed 10 times in total (remeasured after shaking the petri dish once in each time) to define an average value of them as the YI of the polymer particles.
- To an aqueous solution dissolving the modified vinyl alcohol-based polymer particles obtained in any of Examples and Comparative Examples (concentration of 5 mass %), 1 part by mass of 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone as a photoinitiator was added based on 100 parts by mass of the particles and then dissolved to prepare a coating liquid. The coating liquid was cast into a 15 cm×15 cm mold formed by folding the edges of a polyethylene terephthalate film, and the solvent was sufficiently evaporated at room temperature under atmospheric pressure to obtain a film with a thickness of approximately 100 μm. The film was irradiated with ultraviolet rays at an intensity of 10 J/cm2 to prepare an evaluation film and then measure a mass (W2). The evaluation film thus obtained was immersed in a boiling water for 1 hour and then taken out of the water. After vacuum drying at 40° C. for 12 hours, a mass (W1) was measured. From the mass (W1) thus obtained and the mass (W2) of the film before immersion, an elution rate under the boiling conditions was calculated in accordance with a formula below, and the elution rate was used as an index of photosensitivity (a lower elution rate indicates higher photosensitivity). It should be noted that, in the case where an evaluation film was dissolved during immersion in water, it was evaluated as “unmeasurable” and indicated with “-” in Table 1.
-
Elution Rate (mass %)=100×([W2]−[W1])/[W2] - Using a viscometer “LVDV-2+PRO” manufactured by Brookfield, a viscosity η0 immediately after preparing an aqueous solution (concentration of mass %) in which the particles obtained in any of Examples and Comparative Examples and a viscosity η7 7 days after the preparation were respectively measured, followed by calculation of a viscosity ratio η7/η0 to evaluate the viscosity stability by criteria below. A greater viscosity ratio η7/η0 means a greater degree of increase in the viscosity of the solution and poor viscosity stability.
- A: less than 1.3 of η7/η0
- B: 1.3 or more and less than 1.6 of η7/η0
- C: 1.6 or more of η7/η0
- The modified vinyl alcohol-based polymer particles obtained in any of Examples and Comparative Examples were irradiated with electron beams at 150 kGy to impart water resistance by crosslinking. A chromatographic column (having a glass filter, with an inner diameter of 50 mm and an opening diameter from 40 to 50 μm, and a stopcock) was filled with 100 parts by mass of the modified vinyl alcohol-based polymer particles thus crosslinked. The column was then filled with 130 parts by mass of a mixture of methanol/water=9/1 (mass ratio), and then the stopcock was opened to start filtration. The filtrate was recovered and the point when 90% (i.e., 117 parts by mass) of the added mixture was collected as the filtrate was defined as “completion of filtration” and the liquid flow was evaluated by the time taken from start of filtration to completion of filtration.
- A: Filtration Completed in less than 150 seconds
- B: Filtration Completed in 150 seconds or more and less than 300 seconds
- C: Filtration Completed taking 300 seconds or more
- The modified vinyl alcohol-based polymer particles obtained in any of Examples and Comparative Examples were dried at 80° C. for 12 hours and then a sulfur content of the modified vinyl alcohol-based polymer particles was measured using an organic element analyzer 240011 manufactured by PerkinElmer, Inc.
- Into a reactor provided with a stirrer, a reflux condenser, and an inlet port, 482.0 parts by mass of methacrylic acid, 85.1 parts by mass of ion exchange water, 1.3 parts by mass of p-methoxyphenol, and 4.5 parts by mass of 47% sulfuric acid were sequentially charged, and while stirring at room temperature, 100 parts by mass of a commercially available polyvinyl alcohol resin (viscosity-average degree of polymerization of 500, degree of saponification of 98.5 mol %, and average particle diameter of 723 μm) was added and heated, while stirring, to 80° C. and reacted in the state of a slurry for hours. Then, the mixture was cooled to room temperature and the contents were filtrated to recover modified vinyl alcohol-based polymer. The polymer was washed with a large amount of methanol and then dried at 40° C. and 1.3 Pa for 20 hours to obtain target particles. The structural analysis results and the physical property evaluation results of the modified vinyl alcohol-based polymer particles thus obtained are shown in Table 1.
- Into a reactor provided with a stirrer, a reflux condenser, and an inlet port, 510.3 parts by mass of 4-pentenoic acid, 56.7 parts by mass of ion exchange water, 1.3 parts by mass of p-methoxyphenol, and 4.2 parts by mass of paratoluenesulfonic acid monohydrate were sequentially charged, and while stirring at room temperature, 100 parts by mass of a commercially available polyvinyl alcohol resin (viscosity-average degree of polymerization of 1700, degree of saponification of 98.5 mol %, and average particle diameter of 698 μm) was added and heated, while stirring, to 60° C. and reacted in the state of a slurry for 3 hours. Then, posttreatment was performed in the same manner as in Example 1 to obtain target particles. The structural analysis results and the physical property evaluation results of the modified vinyl alcohol-based polymer particles thus obtained are shown in Table 1.
- It should be noted that, as a result of 1H-NMR measurement of the modified vinyl alcohol-based polymer particles thus obtained, the olefin proton peak derived from the unsaturated hydrocarbon group and the methine proton peak of the vinyl ester group were overlapped, and thus it was not possible to calculate the ratio of the three or more consecutive vinyl ester groups. Then, the modified vinyl alcohol-based polymer particles were dissolved (modified vinyl alcohol-based polymer particle content of 5 mass %) in water, and then 1 mol of propanethiol was added per mol of the olefin, and 1 mol of 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone was further added as a photoinitiator per mol of propanethiol. The solution thus prepared was irradiated with ultraviolet rays at an intensity of 3000 mJ/cm2. The solution thus obtained was added to a large amount of methanol to precipitate polymer particles, and then the particles were analyzed by 1H-NMR and this time it was possible to calculate the ratio of the three or more consecutive vinyl ester groups because the olefin proton peak was disappeared due to the addition of thiol.
- Into a reactor provided with a stirrer, a reflux condenser, and an inlet port, 454.2 parts by mass of methacrylic acid, 5.7 parts by mass of acetic acid, 56.7 parts by mass of ion exchange water, 1.3 parts by mass of p-methoxyphenol, and 4.2 parts by mass of paratoluenesulfonic acid monohydrate were sequentially charged, and while stirring at room temperature, 100 parts by mass of a commercially available polyvinyl alcohol resin (viscosity-average degree of polymerization of 1700, degree of saponification of 99.5 mol %, and average particle diameter of 128 μm) was added and heated, while stirring, to 90° C. and reacted in the state of a slurry for 3 hours. Then, posttreatment was performed in the same manner as in Example 1 to obtain target particles. The structural analysis results and the physical property evaluation results of the modified vinyl alcohol-based polymer particles thus obtained are shown in Table 1.
- Into a reactor provided with a stirrer, a reflux condenser, and an inlet port, 510.3 parts by mass of methacrylic acid, 28.4 parts by mass of acetic acid, 28.4 parts by mass of ion exchange water, 1.3 parts by mass of p-methoxyphenol, and 8.1 parts by mass of paratoluenesulfonic acid monohydrate were sequentially charged, and while stirring at room temperature, 100 parts by mass of a commercially available polyvinyl alcohol resin (viscosity-average degree of polymerization of 1700, degree of saponification of 95 mol %, and average particle diameter of 730 μm) was added and heated, while stirring, to 65° C. and reacted in the state of a slurry for 5 hours. Then, posttreatment was performed in the same manner as in Example 1 to obtain target particles. The structural analysis results and the physical property evaluation results of the modified vinyl alcohol-based polymer particles thus obtained are shown in Table 1.
- Into a reactor provided with a stirrer, a reflux condenser, and an inlet port, 493.3 parts by mass of acrylic acid, 17.0 parts by mass of acetic acid, 56.7 parts by mass of ion exchange water, 1.3 parts by mass of p-methoxyphenol, and 4.2 parts by mass of paratoluenesulfonic acid monohydrate were sequentially charged, and while stirring at room temperature, 100 parts by mass of a commercially available polyvinyl alcohol resin (viscosity-average degree of polymerization of 1000, degree of saponification of 98.5 mol %, and average particle diameter of 725 μm) was added and heated, while stirring, to 65° C. and reacted in the state of a slurry for 5 hours. Then, posttreatment was performed in the same manner as in Example 1 to obtain target particles. The structural analysis results and the physical property evaluation results of the modified vinyl alcohol-based polymer particles thus obtained are shown in Table 1.
- Into a reactor provided with a stirrer, a reflux condenser, and an inlet port, 100 parts by mass of a commercially available polyvinyl alcohol resin (viscosity-average degree of polymerization of 1700, degree of saponification of 98.5 mol %, and average particle diameter of 698 μm) was charged, and while stirring at room temperature, a mixture of 58.0 parts by mass of methacrylic acid, 2.0 parts by mass of acetic acid, 6.7 parts by mass of ion exchange water, 0.3 parts by mass of p-methoxyphenol, and 12.6 parts by mass of paratoluenesulfonic acid monohydrate, mixed in advance, was added in small portions. The mixture was sufficiently stirred and uniformly blended into the entire polyvinyl alcohol resin and then heated, while stirring, to 70° C. and reacted in the state of powder for 5 hours. Then, the powder was washed with a large amount of methanol and then dried at 40° C. and 1.3 Pa for 12 hours to obtain target particles. The structural analysis results and the physical property evaluation results of the modified vinyl alcohol-based polymer particles thus obtained are shown in Table 1.
- Into a reactor provided with a stirrer, a reflux condenser, and an inlet port, 564.2 parts by mass of methacrylic acid, 2.8 parts by mass of ion exchange water, 1.3 parts by mass of p-methoxyphenol, and 4.2 parts by mass of paratoluenesulfonic acid monohydrate were sequentially charged, and while stirring at room temperature, 100 parts by mass of a commercially available polyvinyl alcohol resin (viscosity-average degree of polymerization of 500, degree of saponification of 98.5 mol %, and average particle diameter of 720 μm) was added and heated, while stirring, to 80° C. and reacted in the state of a slurry for 5 hours. Then, posttreatment was performed in the same manner as in Example 1 to obtain target particles. The structural analysis results and the physical property evaluation results of the modified vinyl alcohol-based polymer particles thus obtained are shown in Table 1.
- A commercially available polyvinyl alcohol resin (viscosity-average degree of polymerization of 1700, degree of saponification of 98.5 mol %, and average particle diameter of 698 μm) was evaluated. The structural analysis results and the physical property evaluation results are shown in Table 1.
- Into a reactor provided with a stirrer, a reflux condenser, and an inlet port, 400.0 parts by mass of dimethyl sulfoxide, and 100 parts by mass of a commercially available polyvinyl alcohol resin (viscosity-average degree of polymerization of 1700, degree of saponification of 98.5 mol %, and average particle diameter of 698 μm) vacuum dried at 80° C. for 24 hours in advance were added and heated, while stirring, to 100° C. to obtain a homogeneous solution. To the solution, 33.4 parts by mass of methyl methacrylate and 1.1 parts by mass of phenothiazine were added and stirred until homogeneity. To the solution thus obtained, 1.9 parts by mass of sodium acetate was added as a transesterification catalyst and reacted for 5 hours and then left for cooling at room temperature. DMSO was added to the reaction solution for dilution, and then dropped into methanol to isolate the polymer and dried at 40° C. and 1.3 Pa for 12 hours. The structural analysis results and the physical property evaluation results of the modified vinyl alcohol-based polymer particles thus obtained are shown in Table 1.
- Into a reactor provided with a stirrer, a reflux condenser, and an inlet port, 400.0 parts by mass of dimethyl sulfoxide, and 100 parts by mass of a commercially available polyvinyl alcohol resin (viscosity-average degree of polymerization of 500, degree of saponification of 98.5 mol %, and average particle diameter of 723 μm) vacuum dried at 80° C. for 24 hours in advance were added and heated, while stirring, to 100° C. to obtain a homogeneous solution. To the solution, 40.0 parts by mass of 3,3-methyl dimethylpentenoate (MPM) was added and stirred until homogeneity. To the solution thus obtained, 0.4 parts by mass of tetramethylammonium methyl carbonate was added as a transesterification catalyst and reacted for 5 hours and then left for cooling at room temperature. DMSO was added to the reaction solution for dilution, and then dropped into methanol to isolate the polymer and dried at 40° C. and 1.3 Pa for 12 hours. The structural analysis results and the physical property evaluation results of the modified vinyl alcohol-based polymer particles thus obtained are shown in Table 1.
- Into a reactor provided with a stirrer, a reflux condenser, and an inlet port, 288.0 parts by mass of ion exchange water was charged, and 100 parts by mass of a commercially available polyvinyl alcohol resin (viscosity-average degree of polymerization of 500, degree of saponification of 98.5 mol %, and average particle diameter of 723 μm) was added while stirring, heated to 95° C., and heated and stirred for 3 hours to obtain a homogeneous solution. The solution was cooled to room temperature, and 558.0 parts by mass of methacrylic acid, 2 parts by mass of p-methoxyphenol, and 27.0 parts by mass of a 36% aqueous hydrochloric acid solution were sequentially charged while stirring, heated to 80° C. while stirring, and reacted in the state of a homogeneous solution for 2 hours, and then cooled to room temperature. The solution thus obtained was diluted and added in small portions to a large amount of strongly stirred methanol to precipitate the modified vinyl alcohol-based polymer microparticles. The precipitate was recovered and further washed with a large amount of methanol, and then dried at 40° C. and 1.3 Pa for 12 hours to obtain target microparticles. The structural analysis results and the physical property evaluation results of the modified vinyl alcohol-based polymer particles thus obtained are shown in Table 1.
-
TABLE 1 Vinyl Alcohol-Based Polymer Particle (Base Polymer) Degree of Degree of Average Polymer- Saponi- Particle Medium Water Catalyst Reaction Reaction ization fication Diameter (Substrate) Content 1) Type Amount 2) Temperature Time Unit — mol % μm — mass % — mol ° C. h Example 1 500 98.5 723 Methacrylic Acid 15 47% H2SO4 0.01 80 5 Example 2 1700 98.5 698 4-Pentenoic Acid 10 p-TsOH•H2O 0.01 60 3 Example 3 1700 99.5 128 Methacrylic Acid/ 10 p-TsOH•H2O 0.01 90 3 Acetic Acid Example 4 1700 95 730 Methacrylic Acid/ 5 p-TsOH•H2O 0.02 65 5 Acetic Acid Example 5 1000 98.5 725 Acrylic Acid/ 10 p-TsOH•H2O 0.01 65 5 Acetic Acid Example 6 1700 98.5 698 Methacrylic Acid/ 10 p-TsOH•H2O 0.03 70 5 Acetic Acid Example 7 500 98.5 720 Methacrylic Acid 0.5 p-TsOH•H2O 0.01 80 5 Comparative 1700 98.5 698 — — — — — — Example 1 Comparative 1700 98.5 698 Methyl 0.2 AcONa 0.01 105 5 Example 2 Methacrylate/DMSO Comparative 500 98.5 723 MPM/DMSO 0.2 [Me4N][MeOCOO] 0.001 100 5 Example 3 Comparative 500 98.5 723 Methacrylic Acid 35 36% HCl aq. 0.1 80 2 Example 4 Structure of Modified Vinyl Alcohol-Based Polymer Particle Physical Properties of Modified Vinyl Ratio of Three or Average Specific Vinyl Alcohol-Based Polymer Degree of Alcohol Unit More Consecutive Particle Surface Photosensitivity Viscosity Liquid Sulfur Modification Content Vinyl Ester Groups Diameter Area (Elution Rate) Stability Flow Yi Content Unit mol % mol % % μm m2/g mass % — — — ppm Example 1 0.9 99 0.5 725 0.29 6.5 B A 12.5 970 Example 2 3.8 96.1 2.4 710 0.30 13.8 A A 14.0 570 Example 3 1.5 98.4 1.5 125 1.40 2.0 B B 13.8 620 Example 4 1.1 96.0 6.8 703 0.28 5.2 A A 15.5 340 Example 5 1.3 97.2 2.1 685 0.28 3.0 A A 11.5 330 Example 6 2.1 96.4 1.8 680 0.29 2.7 A A 13.5 420 Example 7 0.4 98.1 5.5 700 0.29 10.8 B A 75.0 520 Comparative 0.0 98.5 12.8 698 0.29 — C B 9.0 18 Example 1 Comparative 1.3 97.2 10.5 38 0.40 8.2 C C 20.4 31500 Example 2 Comparative 2.0 97.5 4.1 39 0.41 5.2 A C 51.2 33400 Example 3 Comparative 2.8 97.1 1.9 21 0.44 6.2 A C 11.2 15 Example 4 1) Water Content in Mixed Medium 2) Amount of Catalyst added per mol of Hydroxyl Group in Vinyl Alcohol-Based Polymer - As clearly seen from Examples 1 through 7, the production method of the present invention allows modification without changing the particle shape, and thus allows convenient isolation of the modified vinyl alcohol-based polymer particles without operation of precipitating the reaction product in a poor solvent. The modified vinyl alcohol-based polymer particles of the present invention exhibited high viscosity stability and caused less odor due to the sulfur content when used in the form of an aqueous solution. The modified vinyl alcohol-based polymer particles also had excellent high-energy beam reactivity and had excellent liquid flow when used as a column filler after crosslinking. Moreover, since the production method of the present invention did not use DMSO, it was also possible to suppress contamination of the sulfur content.
- When vinyl alcohol-based polymer particles were reacted by dissolving in a solvent as in Comparative Examples 2 through 4, modified vinyl alcohol-based polymer particles as a reaction product had to be precipitated in a poor solvent for isolation, and thus the operation was complicated and the particle shape was not readily controlled. The unmodified vinyl alcohol-based polymer particles in Comparative Example 1 did not exhibit photosensitivity. The vinyl alcohol-based polymer particles having the ratio of the three or more consecutive vinyl ester groups of more than 10% in Comparative Examples 1 and 2 had low viscosity stability when used in the form of an aqueous solution. As in Comparative Examples 2 through 4, the modified vinyl alcohol-based polymer particles obtained by reacting while the vinyl alcohol-based polymer particles were dissolved had an average particle diameter of less than 50 μm and had poor liquid flow. As in Comparative Examples 2 and 3, use of DMSO during the reaction caused an extremely large content of sulfur in the modified vinyl alcohol-based polymer particles.
- The modified vinyl alcohol-based polymer particles obtained in Example 6 was subjected to evaluation as a column filler. The particles were irradiated with electron beams at 150 kGy for impartation of water resistance by crosslinking. A chromatographic column (having a glass filter with an inner diameter of 50 mm and an opening diameter from 40 to 50 μm and a stopcock) was filled with 100 parts by mass of the modified vinyl alcohol-based polymer particles thus crosslinked and 1000 parts by mass of super dehydrated methanol was flown as an eluate to wet the polymer particles. By the polymer particles in an upper area of the column, super dehydrated methanol containing mass % of ion exchange water was adsorbed, and then 100 parts by mass of super dehydrated methanol was flown as an eluate. The liquid was recovered from a column outlet for analysis.
- During the above test, good liquid flow was maintained. The recovered liquid was analyzed by 1H-NMR and no water was contained in the recovered liquid, and thus it was confirmed that water was retained in the modified vinyl alcohol-based polymer particles. The recovered liquid was subjected to elementary analysis and found that the sulfur content in the recovered liquid was 18 ppm.
Claims (13)
1. A method of producing modified vinyl alcohol-based polymer particles, the method comprising:
mixing vinyl alcohol-based polymer particles with a mixed medium comprising unsaturated carboxylic acid, an acid catalyst, and water, thereby reacting the vinyl alcohol-based polymer particles with the unsaturated carboxylic acid to obtain modified vinyl alcohol-based polymer particles comprising a vinyl ester unit, having a vinyl alcohol unit content based on the total constitutional units from 95 to 99.99 mol %, and having an average particle diameter from 50 to 2000 am,
wherein the unsaturated carboxylic acid is a compound of formula (1):
X denotes a carbon-carbon bond or a divalent saturated hydrocarbon group having a carbon number from 1 to 10 optionally having a branched structure, Y denotes a hydrogen atom or a saturated hydrocarbon group having a carbon number from 1 to 6 optionally having a branched structure, and Z denotes a hydrogen atom or a methyl group, and
the vinyl ester unit is a unit of formula (2):
2. The method according to claim 1 , wherein the modified vinyl alcohol-based polymer particles have a specific surface area of from 0.01 to 1.0 m2/g.
3. The method according to claim 1 , wherein the mixed medium has a water content of from 1 to 30 mass %.
4. The method according to claim 1 , wherein the mixed medium further comprises acetic acid.
5. The method according to claim 1 , wherein Y denotes a hydrogen atom.
6. The method according to claim 1 , wherein X denotes a carbon-carbon bond.
7. The method according to claim 1 , further comprising washing the modified vinyl alcohol-based polymer particles.
8. Modified vinyl alcohol-based polymer particles comprising a vinyl ester unit, wherein a vinyl alcohol unit content is from 95 to 99.99 mol % and a sulfur content is from 0.01 to 20000 ppm based on the total constitutional units, and an average particle diameter is from 50 to 2000 μm, and
wherein the vinyl ester unit is a unit of formula (2):
X denotes a carbon-carbon bond or a divalent saturated hydrocarbon group having a carbon number from 1 to 10 optionally having a branched structure, Y denotes a hydrogen atom or a saturated hydrocarbon group having a carbon number from 1 to 6 optionally having a branched structure, and Z denotes a hydrogen atom or a methyl group.
9. The particles according to claim 8 , wherein a ratio of three or more consecutive vinyl ester units to the total vinyl ester units is 10 mol % or less in the modified vinyl alcohol-based polymer.
10. The particles according to claim 8 , wherein a yellow index (YI) measured in accordance with ASTM D1925 is 50 or less.
11. The particles according to claim 8 , wherein a content of the vinyl ester unit based on the total constitutional units is from 0.01 to 5 mol %.
12. The particles according to claim 8 , wherein Y denotes a hydrogen atom.
13. The particles according to claim 8 , wherein X denotes a carbon-carbon bond.
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WO2020184659A1 (en) | 2020-09-17 |
EP3940004A4 (en) | 2023-05-03 |
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JPWO2020184659A1 (en) | 2020-09-17 |
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KR20210141963A (en) | 2021-11-23 |
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